CN107774281B - Catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, preparation method thereof and method for preparing low-carbon olefin by carbon monoxide hydrogenation - Google Patents

Catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, preparation method thereof and method for preparing low-carbon olefin by carbon monoxide hydrogenation Download PDF

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CN107774281B
CN107774281B CN201610781723.9A CN201610781723A CN107774281B CN 107774281 B CN107774281 B CN 107774281B CN 201610781723 A CN201610781723 A CN 201610781723A CN 107774281 B CN107774281 B CN 107774281B
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carbon monoxide
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hydrogenation
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CN107774281A (en
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张晓昕
王宣
慕旭宏
宗保宁
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • C07C1/044—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof containing iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0455—Reaction conditions
    • C07C1/046—Numerical values of parameters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/04—Sulfides
    • C07C2527/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • C07C2527/051—Molybdenum
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, a preparation method thereof and a method for preparing low-carbon olefin by carbon monoxide hydrogenation, wherein the catalyst comprises a porous amorphous alloy framework and a molybdenum component loaded on the porous amorphous alloy framework, the porous amorphous alloy framework comprises iron and silicon, and the molybdenum component is molybdenum sulfide and/or a precursor of molybdenum sulfide; wherein, based on the total weight of the catalyst and element weight, the content of iron in the catalyst is 45-95 wt%, the content of silicon is 3-40 wt%, the content of molybdenum is 1-10 wt%, and the content of sulfur is 0.1-5 wt%. The method of the invention is adopted to prepare the low-carbon olefin by hydrogenating the carbon monoxide, and the selectivity of the low-carbon olefin is good.

Description

Catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, preparation method thereof and method for preparing low-carbon olefin by carbon monoxide hydrogenation
Technical Field
The invention relates to a catalyst for preparing low-carbon olefin by hydrogenation of carbon monoxide, a preparation method thereof and a method for preparing low-carbon olefin by hydrogenation of carbon monoxide.
Background
Lower olefins (C)2-C4Olefins) as basic organic chemical raw materials, play a vital role in modern petroleum and chemical industries. Particularly ethylene and propylene, with the increasing demand and the expanding application field, the synthesis method thereof is carried outExtensive research is increasingly important.
The methods for preparing low-carbon olefins can be generally divided into two major categories, one is the petroleum route and the other is the non-petroleum route. So far, the traditional light oil cracking method, namely the petroleum route, is mainly adopted in the world to prepare low-carbon olefins such as ethylene, propylene and the like. Under the condition of rising petroleum price, the method for directly or indirectly preparing the low-carbon olefin by using the natural gas as the raw material through the synthesis gas has technical and economic attractions. For example, the technology of preparing low-carbon olefin by taking natural gas as a raw material and adopting methods such as oxidative coupling and the like, the technology of preparing synthesis gas by taking natural gas or coal as a raw material, the technology of preparing low-carbon olefin by Fischer-Tropsch synthesis (direct method) or methanol or dimethyl ether (indirect method) by synthesis gas and the like. The process for directly preparing the low-carbon olefin from the synthesis gas is a process for generating a target product by one-step reaction, and the process flow is simpler and more economic than an indirect method.
The catalyst for the reaction of directionally converting the synthesis gas into the low-carbon olefin generally selects Fe as an active component, and is added with some auxiliary agents; the support for the catalyst is typically various types of molecular sieves and activated carbon. Wherein, the molecular sieve supported catalyst can realize the shape selection of the product through the adjustable pore channel structure of the molecular sieve, and is concerned about improving the selectivity of the low-carbon olefin.
Chinese patent CN1260823A by exxon corporation reports a method for converting synthesis gas to lower olefins using modified molecular sieves, which uses Fe3(CO)12ZSM-5 modified molecular sieve catalyst, H at 260 deg.C2Volume ratio of/CO of 3 and GHSV of 1000h-1The total selectivity of ethylene and propylene was 65% under the reaction conditions of (1).
Chinese patent CN92109866.9 of the institute of chemical and physical research reports that the use of a high-silicon molecular sieve to load active components such as Fe-Mn realizes better selectivity of synthesis gas to prepare low-carbon olefin. The catalyst disclosed is a ferro-manganese metal oxide-molecular sieve (K-Fe-MnO/Silicalite-2) composite catalyst, the CO conversion rate reaches 70-90%, and C2-C4The olefin selectivity was 72-74%.
However, the pore structure of the molecular sieve is changed in the process of loading active components on the molecular sieve, and the active metal on the outer surface is not influenced by the pore structure of the carrier, so that high selectivity is obtained, and the function of the carrier cannot be fully exerted.
Chinese invention patents ZL03109585.2 and CN101219384A of Beijing university of chemical industry disclose Fe/activated carbon catalysts which take activated carbon as a carrier and manganese, copper, zinc, silicon, potassium and the like as auxiliary agents, are used for the reaction of preparing low-carbon olefin from synthesis gas, and have the temperature of 300 ℃ and the pressure of 1-2MPa and the space velocity of the synthesis gas of 400 ℃ for 1000 h--1Under the condition of no raw material gas circulation, the CO conversion rate can reach 95%, the content of hydrocarbon in gas-phase products is 69.5%, and the selectivity of ethylene, propylene and butylene in hydrocarbon can reach more than 68%. However, the catalyst is seriously coked during use and cannot be operated for a long time.
De Jong et al (Science, 2012, 335, 835) disperse iron nanoparticles uniformly on weak interactive alpha-alumina or carbon nanofiber supports to convert synthesis gas directly to produce C2～C4The light olefin accounts for 50% of the mass content of the hydrocarbon product when the CO conversion rate is 80%, and has relatively good anti-coking performance, but the preparation process of the catalyst is complex and difficult to realize industrial application.
For many years, some research teams have attempted to develop high temperature molten iron catalysts for increasing the selectivity of products from fischer-tropsch synthesis for direct production of lower olefins.
Chinese patent CN101757925A provides a molten iron catalyst for producing low-carbon olefin from synthesis gas, which is composed of iron oxide and promoters such as alumina, calcium oxide and potassium oxide, and has high Fischer-Tropsch synthesis activity and selectivity, a single-pass conversion rate of more than 95%, methane selectivity of less than 10% and low-carbon olefin content of more than 35%. However, the poor mechanical properties of the molten iron catalyst at high temperature may cause the blockage of the catalyst bed in the fixed bed operation or cause the fouling of the separation equipment in the fluidized bed process, and the application of the molten iron catalyst in the reaction process of producing low-carbon olefins by fischer-tropsch synthesis is limited.
In addition, these catalysts encounter varying degrees of difficulty in the procedures of preparation repeatability, scale-up preparation, etc. Therefore, the catalyst with a novel structure is designed, high selectivity of the low-carbon olefin is obtained, and the catalyst has important significance for industrial application of preparing the low-carbon olefin from the synthesis gas.
Disclosure of Invention
The invention aims to provide a catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, a preparation method thereof and a method for preparing low-carbon olefin by carbon monoxide hydrogenation.
In order to achieve the above object, the present invention provides a catalyst for preparing low carbon olefin by hydrogenation of carbon monoxide, the catalyst comprising a porous amorphous alloy skeleton and a molybdenum component loaded on the porous amorphous alloy skeleton, wherein the porous amorphous alloy skeleton comprises iron and silicon, and the molybdenum component is molybdenum sulfide and/or a precursor of molybdenum sulfide; wherein, based on the total weight of the catalyst and element weight, the content of iron in the catalyst is 45-95 wt%, the content of silicon is 3-40 wt%, the content of molybdenum is 1-10 wt%, and the content of sulfur is 0.1-5 wt%.
Preferably, the porous amorphous alloy framework further comprises 0.1-40 wt% of a metal M, based on the total weight of the catalyst and by weight of elements, the metal M being at least one selected from the group consisting of group IB metals, group IIB metals, group IIIB metals, group IVB metals, group VIB metals, group VIIB metals and group VIII metals.
Preferably, the metal M is at least one selected from cobalt, manganese, copper and cerium.
Preferably, the catalyst contains 70-85 wt% of iron, 10-25 wt% of silicon, 1-3 wt% of molybdenum and 2-4 wt% of sulfur, based on the total weight of the catalyst and calculated by element weight.
The invention also provides a preparation method of the catalyst for preparing the low-carbon olefin by hydrogenating the carbon monoxide, which comprises the following steps: a. mixing and melting alloy framework raw materials including iron and silicon, and then quenching to obtain a master alloy; b. b, extracting and desilicifying the master alloy obtained in the step a to obtain a porous amorphous alloy framework; c. loading a precursor of molybdenum sulfide on the porous amorphous alloy skeleton obtained in the step b to obtain a catalyst for preparing low-carbon olefin by hydrogenation of carbon monoxide; wherein, based on the total weight of the catalyst and element weight, the content of iron in the catalyst is 45-95 wt%, the content of silicon is 3-40 wt%, the content of molybdenum is 1-10 wt%, and the content of sulfur is 0.1-5 wt%.
Preferably, the alloy framework raw material further comprises a metal M, wherein the metal M is at least one selected from group IB metals, group IIB metals, group IIIB metals, group IVB metals, group VIB metals, group VIIB metals and group VIII metals, and the content of the metal M in the catalyst is 0.1-40 wt% based on the total weight of the catalyst and calculated by the weight of elements.
Preferably, the metal M is at least one selected from cobalt, manganese, copper and cerium.
Preferably, the quenching treatment in step a comprises: spraying the mixed molten liquid of the alloy skeleton raw material onto a copper roller which is 600-inch sand with 1000 revolutions per minute and is filled with cooling water, cooling the mixed molten liquid at the cooling speed of 1000-inch sand with 1600 ℃/second and throwing the mixed molten liquid along the tangent line of the copper roller, and crushing the obtained flaky strip alloy to 20-200 meshes to obtain the master alloy; the step of extracting and desiliconizing in the step b comprises the following steps: b, performing alkali liquor extraction desilication on the master alloy obtained in the step a in an alkali liquor to obtain an alkali liquor extraction desilication alloy; carrying out acid liquor extraction desilication on the obtained alkali liquor extraction desilication alloy in acid liquor to obtain the porous amorphous alloy framework; wherein the conditions of alkali liquor extraction and desilication are as follows: the temperature is 0-100 ℃, the time is 10-60 minutes, the molar concentration of the alkali liquor is 1-12 mol/L, the alkali in the alkali liquor is sodium hydroxide and/or potassium hydroxide, and the weight ratio of the master alloy to the alkali in the alkali liquor is 1: (1-10); the conditions of acid liquor extraction and desilication are as follows: the temperature is 0-100 ℃, the time is 10-120 minutes, the molar concentration of the acid liquid is 1-12 mol/L, the acid in the acid liquid is hydrochloric acid and/or nitric acid, and the weight ratio of the master alloy to the acid in the acid liquid is 1: (0.4-10); the loading method in the step c is a precipitation method and/or an impregnation method.
Preferably, the step of loading the precursor of molybdenum sulfide on the porous amorphous alloy skeleton obtained in the step b in the step c comprises the following steps: and c, mixing the porous amorphous alloy skeleton in the step b with an ammonium thiomolybdate solution, adding ammonia water to precipitate ammonium thiomolybdate on the porous amorphous alloy skeleton, and roasting the porous amorphous alloy skeleton attached with the precipitate to obtain the catalyst for preparing the low-carbon olefin by carbon monoxide hydrogenation.
The invention also provides a method for preparing low-carbon olefin by hydrogenation of carbon monoxide, which comprises the following steps: the carbon monoxide is contacted with the catalyst for preparing the low-carbon olefin by hydrogenating the carbon monoxide, and the low-carbon olefin is prepared by hydrogenating in a hydrogenation reactor under the hydrogenation condition.
Preferably, the hydrogenation conditions include: the temperature is 200 ℃ and 500 ℃, the pressure is 0.5-15.0 MPa, and the gas volume space velocity is 500 ℃ and 100000 hours-1The molar ratio of hydrogen to carbon monoxide is 0.5-10; the hydrogenation reactor is at least one selected from a slurry bed reactor, a fluidized bed reactor and a fixed bed reactor.
The catalyst of the invention has simple preparation method, uniform particle size distribution and controllable structure. When the catalyst is applied to the preparation of low-carbon olefin by carbon monoxide hydrogenation, the catalytic efficiency, stability and activity are high, the selectivity of the low-carbon olefin is high, and the selectivity of carbon dioxide is low.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation, which comprises a porous amorphous alloy framework and a molybdenum component loaded on the porous amorphous alloy framework, wherein the porous amorphous alloy framework comprises iron and silicon, and the molybdenum component is molybdenum sulfide and/or a precursor of molybdenum sulfide; wherein, based on the total weight of the catalyst and element weight, the content of iron in the catalyst is 45-95 wt%, the content of silicon is 3-40 wt%, the content of molybdenum is 1-10 wt%, and the content of sulfur is 0.1-5 wt%; preferably, the catalyst contains 70-85 wt% of iron, 10-25 wt% of silicon, 1-3 wt% of molybdenum and 2-4 wt% of sulfur, based on the total weight of the catalyst and calculated by element weight. The molybdenum sulfide in the molybdenum component is typically present as a simple substance or mixture of molybdenum monosulfide, molybdenum disulfide, molybdenum trisulfide.
According to the present invention, the porous amorphous alloy skeleton is well known to those skilled in the art, and belongs to an amorphous alloy, the arrangement of its internal atoms is free from the defects of grain boundary, dislocation, segregation, etc. which are usually existed in the crystalline alloy, and the constituent elements are connected by metal bonds and maintain short-range order and long-range disorder within a range of several lattice constants, so as to form a structure similar to an atomic cluster. The porous amorphous alloy framework may further comprise 0.1-40 wt% of a metal M, preferably 0.5-20 wt% of a metal M, based on the total weight of the catalyst and by weight of the elements, which may be at least one selected from group IB metals, group IIB metals, group IIIB metals, group IVB metals, group VIB metals, group VIIB metals and group VIII metals, preferably at least one selected from cobalt, manganese, copper and cerium.
According to the invention, the catalyst can exist in a shell-core structure, a porous amorphous alloy framework is taken as a core, and a molybdenum component is taken as a shell coated on the framework.
The invention also provides a preparation method of the catalyst for preparing the low-carbon olefin by hydrogenating the carbon monoxide, which comprises the following steps: a. mixing and melting alloy framework raw materials including iron and silicon, and then quenching to obtain a master alloy; b. b, extracting and desilicifying the master alloy obtained in the step a to obtain a porous amorphous alloy framework; c. loading a precursor of molybdenum sulfide on the porous amorphous alloy skeleton obtained in the step b to obtain a catalyst for preparing low-carbon olefin by hydrogenation of carbon monoxide; wherein, based on the total weight of the catalyst and element weight, the content of iron in the catalyst is 45-95 wt%, the content of silicon is 3-40 wt%, the content of molybdenum is 1-10 wt%, and the content of sulfur is 0.1-5 wt%.
According to the present invention, the preparation method of the porous amorphous alloy skeleton is well known to those skilled in the art, and can be prepared by a quenching method, a chemical reaction method, an electrodeposition method, etc., and since the preparation method of the catalyst of the present invention includes an extraction desilication step, the charge amount of the components other than silicon is almost the same as the actual content of the catalyst, and those skilled in the art can control the content of silicon in the catalyst by the conditions of extraction desilication, or calculate the charge amount of silicon according to the target content of silicon in the catalyst and the conditions of extraction desilication.
According to the invention, the alloy skeleton raw material may further include a metal M, the metal M is at least one selected from group IB metals, group IIB metals, group IIIB metals, group IVB metals, group VIB metals, group VIIB metals and group VIII metals, preferably at least one selected from cobalt, manganese, copper and cerium, and the content of the metal M in the catalyst may be 0.1 to 40 wt%, preferably 0.5 to 20 wt%, more preferably 3 to 10 wt%, based on the total weight of the catalyst and calculated by the element weight.
Quenching treatment, extraction desilication and loading are well known to those skilled in the art according to the present invention, for example, the quenching treatment in step a may comprise: spraying the mixed molten liquid of the alloy skeleton raw material onto a copper roller which is 600-inch sand-baked at 1000 rpm and is filled with cooling water, cooling the mixed molten liquid at the cooling speed of 1000-inch sand-baked at 1600 ℃/s and throwing the mixed molten liquid along the tangent line of the copper roller, and crushing the obtained scaly strip alloy into 20-200 meshes to obtain the master alloy, wherein the copper roller can be a double roller or a single roller, the spraying can be in an atomizing spraying mode, preferably the atomizing spraying at the temperature of more than 1300 ℃, and the size of the master alloy is 80-200 meshes; the step of extraction desilication in step b may comprise: b, performing alkali liquor extraction desilication on the master alloy obtained in the step a in an alkali liquor to obtain an alkali liquor extraction desilication alloy; the dark gray alkali liquor extraction desilication alloy can be washed by distilled water until the pH value is less than 10, and then the obtained alkali liquor extraction desilication alloy is subjected to acid liquor extraction desilication in acid liquor to obtain the porous amorphous alloy framework; wherein, the conditions of the alkali liquor extraction desilication can be as follows: the reaction can be carried out under magnetic stirring, the temperature can be 0-100 ℃, preferably 25-100 ℃, the time can be 10-60 minutes, preferably 20-60 minutes, the molar concentration of the alkali liquor can be 1-12 mol/L, preferably 2-10 mol/L, the alkali in the alkali liquor can be sodium hydroxide and/or potassium hydroxide, and the weight ratio of the master alloy to the alkali in the alkali liquor can be 1: (1-10); the conditions of acid liquor extraction desilication can be as follows: the temperature may be 0-100 ℃, preferably 50-100 ℃, the time may be 10-120 minutes, preferably 40-120 minutes, the molar concentration of the acid solution may be 1-12 moles/liter, the acid in the acid solution may be hydrochloric acid and/or nitric acid, and the weight ratio of the master alloy to the acid in the acid solution may be 1: (0.4-10); in addition, according to the conventional requirement of porous amorphous alloy framework loading, after acid liquor extraction and desilication, the method can also comprise the step of washing the porous amorphous alloy framework by using distilled water until the washing water is neutral, and the washed porous amorphous alloy framework can be stored under the protection of inert gas or hydrogen; the loading method in step c may be a precipitation method and/or an impregnation method, which are well known to those skilled in the art, for example, the step of loading the precursor of molybdenum sulfide on the porous amorphous alloy skeleton obtained in step b in step c may include: and c, mixing the porous amorphous alloy skeleton in the step b with an ammonium thiomolybdate solution, adding ammonia water to precipitate ammonium thiomolybdate on the porous amorphous alloy skeleton, and roasting the porous amorphous alloy skeleton attached with the precipitate to obtain the catalyst for preparing the low-carbon olefin by carbon monoxide hydrogenation. A specific embodiment is that a porous amorphous alloy framework is contacted with 1-5 wt% ammonium thiomolybdate aqueous solution at 60-80 ℃, the contact time can be 0.5-2 hours, 5-10 wt% ammonia water is dripped to adjust the pH value to form complete black precipitate, the precipitate is kept stand and aged for 6-10 hours, the precipitate is filtered and washed by deionized water, the precipitate is dried in a vacuum at 50-100 ℃ for 2-6 hours and then is placed in a tubular furnace to be heated to 400 ℃ under the protection of nitrogen, and the catalyst is prepared by thermal decomposition for 2-6 hours.
The invention also provides a method for preparing low-carbon olefin by hydrogenation of carbon monoxide, which comprises the following steps: the carbon monoxide is contacted with the catalyst for preparing the low-carbon olefin by hydrogenating the carbon monoxide, and the low-carbon olefin is prepared by hydrogenating in a hydrogenation reactor under the hydrogenation condition.
The methods and conditions for the hydrogenation of carbon monoxide to lower olefins according to the present invention are well known to those skilled in the art, and may include, for example: the temperature is 200 ℃ and 500 ℃, the pressure is 0.5-15.0 MPa, and the gas volume space velocity is 500 ℃ and 100000 hours-1The molar ratio of hydrogen to carbon monoxide is 0.5-10; the hydrogenation reactor may be at least one selected from a slurry bed reactor, a fluidized bed reactor and a fixed bed reactor.
The present invention will be illustrated by the following examples, but the present invention is not limited thereto.
The contents of the respective components of the catalysts prepared in examples 1 to 5 were measured by plasma emission spectroscopy (ICP).
The gas products obtained in examples 6 to 10 were measured by gas chromatography using a TCD detector, and the liquid products were measured by gas chromatography using a FID detector. Hydrocarbon selectivity refers to the weight fraction of hydrocarbons in the reaction product.
Examples 1-5 illustrate methods for providing the catalyst preparation of the present invention and the catalysts prepared.
Example 1
Adding 1.5 kg of iron and 1.5 kg of silicon into a graphite crucible, heating the graphite crucible in a high-frequency furnace until the graphite crucible is melted, then spraying the molten liquid onto a copper roller with the rotating speed of 600 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the alloy liquid at the cooling speed of 1000-1600 ℃/second, throwing the alloy liquid into the water along the tangent line of the copper roller to form a scaly strip, and grinding the scaly strip until the particle diameter is below 500 micrometers to obtain the master alloy. 50g of the master alloy was slowly added to a three-necked flask containing 500 g of a 20 wt% aqueous solution of sodium hydroxide, and the temperature was controlled to 60 ℃ and stirred at a constant temperature for 1 hour. Stopping heating and stirring, filtering out liquid, and adding distilled water to wash until the pH value is less than 10; then adding the mixture into 100 g of 20 wt% HCl solution, controlling the temperature to 80 ℃, stirring the mixture at constant temperature for 1 hour, and washing the mixture with distilled water at 80 ℃ until the pH value is 7 to obtain the porous amorphous alloy framework.
Weighing 2g of ammonium thiomolybdate, dissolving in 98ml of deionized water, heating to 60 ℃, adding the porous amorphous alloy skeleton into the ammonium thiomolybdate solution, stirring for 1h, and slowly dropwise adding 10% ammonia water solution to adjust the pH value to about 6. And (2) precipitating at 60 ℃, standing and aging for 8h, filtering, washing with deionized water to be neutral, drying the precipitate in a vacuum drying oven at 80 ℃, putting the dried precipitate in a tubular furnace, introducing nitrogen to protect and heat to above 300 ℃ for decomposition to obtain the catalyst for preparing the low-carbon olefin by hydrogenation of carbon monoxide, wherein the catalyst is numbered as catalyst-1, and the composition is shown in Table 1.
Example 2
Adding 1.5 kg of iron, 1.0 kg of silicon and 0.1 kg of cobalt into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, spraying the molten liquid onto a copper roller with the rotation speed of 900 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the alloy liquid at the cooling speed of 1000-1600 ℃/second, throwing the alloy liquid into the water along the tangent line of the copper roller to form a flaky strip, and grinding the flaky strip until the particle diameter is below 500 micrometers to obtain the master alloy. 50g of the master alloy was slowly added to a three-necked flask containing 500 g of a 20 wt% aqueous solution of sodium hydroxide, and the temperature was controlled to 60 ℃ and stirred at a constant temperature for 1 hour. Stopping heating and stirring, filtering out liquid, and adding distilled water to wash until the pH value is less than 10; then adding the mixture into 100 g of 20 wt% nitric acid solution, controlling the temperature to 80 ℃, stirring the mixture at constant temperature for 1 hour, and washing the mixture with distilled water at 80 ℃ until the pH value is 7 to obtain the porous amorphous alloy framework.
Weighing 2g of ammonium thiomolybdate, dissolving in 98ml of deionized water, heating to 60 ℃, adding the porous amorphous alloy skeleton into the ammonium thiomolybdate solution, stirring for 1h, and slowly dropwise adding 10% ammonia water solution to adjust the pH value to about 6. And (2) precipitating at 60 ℃, standing and aging for 8h, filtering, washing with deionized water to be neutral, drying the precipitate in a vacuum drying oven at 80 ℃, putting the dried precipitate in a tubular furnace, introducing nitrogen to protect and heat to above 300 ℃ for decomposition to obtain the catalyst for preparing the low-carbon olefin by hydrogenation of carbon monoxide, wherein the catalyst is numbered as catalyst-2, and the composition is shown in Table 1.
Example 3
Adding 1.5 kg of iron, 1.5 kg of silicon and 0.2 kg of manganese into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, then spraying the molten liquid onto a copper roller with the rotating speed of 1000 rpm from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the alloy liquid at the cooling speed of 1000 plus one 1600 ℃/s, throwing the alloy liquid into the water along the tangent line of the copper roller to form a flaky strip, and grinding the flaky strip until the particle diameter is below 500 micrometers to obtain the master alloy. 50g of the master alloy was slowly added to a three-necked flask containing 500 g of a 20 wt% aqueous solution of sodium hydroxide, and the temperature was controlled to 60 ℃ and stirred at a constant temperature for 1 hour. Stopping heating and stirring, filtering out liquid, and adding distilled water to wash until the pH value is less than 10; then 100 g of 20 wt% HNO was added3And (3) controlling the temperature in the solution to be 80 ℃, stirring the solution at the constant temperature for 1 hour, and washing the solution with distilled water at the temperature of 80 ℃ until the pH value is 7 to obtain the porous amorphous alloy framework.
Weighing 2g of ammonium thiomolybdate, dissolving in 98ml of deionized water, heating to 60 ℃, adding the porous amorphous alloy skeleton into the ammonium thiomolybdate solution, stirring for 1h, and slowly dropwise adding 10% ammonia water solution to adjust the pH value to about 6. And (2) precipitating at 60 ℃, standing and aging for 8h, filtering, washing with deionized water to be neutral, drying the precipitate in a vacuum drying oven at 80 ℃, putting the dried precipitate in a tubular furnace, introducing nitrogen to protect and heat to above 300 ℃, and decomposing to obtain the catalyst for preparing the low-carbon olefin by hydrogenation of carbon monoxide, wherein the catalyst is numbered as catalyst-3, and the composition is shown in Table 1.
Example 4
Adding 1.5 kg of iron, 1.5 kg of silicon and 0.2 kg of copper into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, then spraying the molten liquid onto a copper roller with the rotating speed of 800 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the alloy liquid at the cooling speed of 1000-1600 ℃/second, throwing the alloy liquid into the water along the tangent line of the copper roller to form a flaky strip, and grinding the flaky strip until the particle diameter is below 500 micrometers to obtain the master alloy. 50g of the master alloy was slowly added to a three-necked flask containing 500 g of a 20 wt% aqueous solution of sodium hydroxide, and the temperature was controlled to 60 ℃ and stirred at a constant temperature for 1 hour. Stopping heating and stirring, filtering out liquid, and adding distilled water to wash until the pH value is less than 10; then adding the mixture into 100 g of 20 wt% HCl solution, controlling the temperature to 80 ℃, stirring the mixture at constant temperature for 1 hour, and washing the mixture with distilled water at 80 ℃ until the pH value is 7 to obtain the porous amorphous alloy framework.
Weighing 2g of ammonium thiomolybdate, dissolving in 98ml of deionized water, heating to 60 ℃, adding the porous amorphous alloy skeleton into the ammonium thiomolybdate solution, stirring for 1h, and slowly dropwise adding 10% ammonia water solution to adjust the pH value to about 6. And (2) precipitating at 60 ℃, standing and aging for 8h, filtering, washing with deionized water to be neutral, drying the precipitate in a vacuum drying oven at 80 ℃, putting the dried precipitate in a tubular furnace, introducing nitrogen to protect, heating to above 300 ℃, and decomposing to obtain the catalyst for preparing the low-carbon olefin by hydrogenation of carbon monoxide, wherein the catalyst is numbered as catalyst-4, and the composition is shown in table 1.
Example 5
Adding 1.5 kg of iron, 1.5 kg of silicon and 0.2 kg of cerium into a graphite crucible, heating the graphite crucible in a high-frequency furnace to be molten, then spraying the molten liquid onto a copper roller with the rotating speed of 600 revolutions per minute from a crucible nozzle, introducing cooling water into the copper roller, rapidly cooling the alloy liquid at the cooling speed of 1000-1600 ℃/second, throwing the alloy liquid into the water along the tangent line of the copper roller to form a flaky strip, and grinding the flaky strip until the particle diameter is below 500 micrometers to obtain the master alloy. 50g of the master alloy was slowly added to a three-necked flask containing 500 g of a 20 wt% aqueous solution of sodium hydroxide, and the temperature was controlled to 60 ℃ and stirred at a constant temperature for 1 hour. Stopping heating and stirring, filtering out liquid, and adding distilled water to wash until the pH value is less than 10; then adding the mixture into 100 g of 20 wt% HCl solution, controlling the temperature to 80 ℃, stirring the mixture at constant temperature for 1 hour, and washing the mixture with distilled water at 80 ℃ until the pH value is 7 to obtain the porous amorphous alloy framework.
Weighing 2g of ammonium thiomolybdate, dissolving in 98ml of deionized water, heating to 60 ℃, adding the porous amorphous alloy skeleton into the ammonium thiomolybdate solution, stirring for 1h, and slowly dropwise adding 10% ammonia water solution to adjust the pH value to about 6. And (2) precipitating at 60 ℃, standing and aging for 8h, filtering, washing with deionized water to be neutral, drying the precipitate in a vacuum drying oven at 80 ℃, putting the dried precipitate in a tubular furnace, introducing nitrogen to protect, heating to above 300 ℃, and decomposing to obtain the catalyst for preparing the low-carbon olefin by hydrogenation of carbon monoxide, wherein the catalyst is numbered as catalyst-5, and the composition is shown in table 1.
Examples 6-10 provide methods of the present invention for the hydrogenation of carbon monoxide to lower olefins.
Examples 6 to 10
Examples 6 to 10 of the present invention, in which the catalysts provided in examples 1 to 5 of the present invention were used to hydrogenate carbon monoxide to produce light olefins in a fixed bed reactor under the same reaction conditions, the specific reaction results are shown in table 2, and the specific reaction conditions are as follows: catalyst loading 0.5 g, reaction temperature 340 deg.C, reaction pressure 2.0 MPa, hydrogen-carbon monoxide molar ratio 2, gas volume space velocity 6000 hr-1。
As can be seen from Table 2, the method of the present invention for hydrogenation of carbon monoxide to produce lower olefins has high CO conversion rate and good selectivity of lower olefins.
TABLE 1
Figure DEST_PATH_IMAGE002
TABLE 2
Examples Example 6 Example 7 Example 8 Example 9 Example 10
Catalyst numbering Catalyst-1 Catalyst-2 Catalyst-3 Catalyst-4 Catalyst-5
Conversion of CO, wt% 84.1 84.8 87.1 89.7 88.4
CO2Selectivity, weight% 5.7 6.2 7.3 7.7 6.4
Hydrocarbon selectivity, weight%
CH4 12.4 11.6 13.7 12.2 11.7
C2H4 21.3 19.4 21.3 16.7 20.3
C2H6 2.7 4.1 3.8 4.4 4.8
C3H6 24.5 19.1 18.7 17.8 19.1
C3H8 5.2 5.7 5.5 6.2 5.8
C4H8 13.1 15.6 14.1 15.7 13.5
C4H10 3.4 4.5 5.2 5.6 4.7
C5 + 17.4 20.0 17.7 21.4 20.1
Total up to 100 100 100 100 100

Claims (11)

1. A catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation comprises a porous amorphous alloy framework and a molybdenum component loaded on the porous amorphous alloy framework, wherein the porous amorphous alloy framework comprises iron and silicon, and the molybdenum component is molybdenum sulfide and/or a precursor of molybdenum sulfide; wherein, based on the total weight of the catalyst and element weight, the content of iron in the catalyst is 45-95 wt%, the content of silicon is 3-40 wt%, the content of molybdenum is 1-10 wt%, and the content of sulfur is 0.1-5 wt%.
2. The catalyst of claim 1, wherein the porous amorphous alloy framework further comprises 0.1-40 wt% of a metal M, based on the total weight of the catalyst and by weight of elements, the metal M being at least one selected from the group consisting of group IB metals, group IIB metals, group IIIB metals, group IVB metals, group VIB metals, group VIIB metals, and group VIII metals.
3. The catalyst according to claim 2, wherein the metal M is at least one selected from cobalt, manganese, copper and cerium.
4. The catalyst of claim 1, wherein the catalyst comprises iron in an amount of 70 to 85 wt%, silicon in an amount of 10 to 25 wt%, molybdenum in an amount of 1 to 3 wt%, and sulfur in an amount of 2 to 4 wt%, based on the total weight of the catalyst and based on the weight of the elements.
5. A preparation method of a catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation comprises the following steps:
a. mixing and melting alloy framework raw materials including iron and silicon, and then quenching to obtain a master alloy;
b. b, extracting and desilicifying the master alloy obtained in the step a to obtain a porous amorphous alloy framework;
c. loading a precursor of molybdenum sulfide on the porous amorphous alloy skeleton obtained in the step b to obtain a catalyst for preparing low-carbon olefin by hydrogenation of carbon monoxide;
wherein, based on the total weight of the catalyst and element weight, the content of iron in the catalyst is 45-95 wt%, the content of silicon is 3-40 wt%, the content of molybdenum is 1-10 wt%, and the content of sulfur is 0.1-5 wt%.
6. The preparation method of claim 5, wherein the alloy framework raw material further comprises a metal M, wherein the metal M is at least one selected from group IB metals, group IIB metals, group IIIB metals, group IVB metals, group VIB metals, group VIIB metals and group VIII metals, and the content of the metal M in the catalyst is 0.1-40 wt% based on the total weight of the catalyst and calculated by the weight of elements.
7. The production method according to claim 6, wherein the metal M is at least one selected from cobalt, manganese, copper, and cerium.
8. The production method according to claim 5, wherein the quenching treatment in step a comprises: spraying the mixed molten liquid of the alloy skeleton raw material onto a copper roller which is 600-inch sand with 1000 revolutions per minute and is filled with cooling water, cooling the mixed molten liquid at the cooling speed of 1000-inch sand with 1600 ℃/second and throwing the mixed molten liquid along the tangent line of the copper roller, and crushing the obtained flaky strip alloy to 20-200 meshes to obtain the master alloy;
the step of extracting and desiliconizing in the step b comprises the following steps: b, performing alkali liquor extraction desilication on the master alloy obtained in the step a in an alkali liquor to obtain an alkali liquor extraction desilication alloy; carrying out acid liquor extraction desilication on the obtained alkali liquor extraction desilication alloy in acid liquor to obtain the porous amorphous alloy framework; wherein the conditions of alkali liquor extraction and desilication are as follows: the temperature is 0-100 ℃, the time is 10-60 minutes, the molar concentration of the alkali liquor is 1-12 mol/L, the alkali in the alkali liquor is sodium hydroxide and/or potassium hydroxide, and the weight ratio of the master alloy to the alkali in the alkali liquor is 1: (1-10); the conditions of acid liquor extraction and desilication are as follows: the temperature is 0-100 ℃, the time is 10-120 minutes, the molar concentration of the acid liquid is 1-12 mol/L, the acid in the acid liquid is hydrochloric acid and/or nitric acid, and the weight ratio of the master alloy to the acid in the acid liquid is 1: (0.4-10);
the loading method in the step c is a precipitation method and/or an impregnation method.
9. The preparation method according to claim 5, wherein the step of loading the precursor of molybdenum sulfide on the porous amorphous alloy skeleton obtained in the step b in the step c comprises the following steps: and c, mixing the porous amorphous alloy skeleton in the step b with an ammonium thiomolybdate solution, adding ammonia water to precipitate ammonium thiomolybdate on the porous amorphous alloy skeleton, and roasting the porous amorphous alloy skeleton attached with the precipitate to obtain the catalyst for preparing the low-carbon olefin by carbon monoxide hydrogenation.
10. A method for preparing low-carbon olefin by hydrogenation of carbon monoxide comprises the following steps: contacting carbon monoxide with the catalyst for preparing the lower olefins by hydrogenating the carbon monoxide according to any one of claims 1 to 4, and hydrogenating the carbon monoxide in a hydrogenation reactor under hydrogenation conditions to prepare the lower olefins.
11. The method for producing lower olefins by hydrogenation of carbon monoxide according to claim 10, wherein the hydrogenation conditions comprise: the temperature is 200 ℃ and 500 ℃, the pressure is 0.5-15.0 MPa, and the gas volume space velocity is 500 ℃ and 100000 hours-1The molar ratio of hydrogen to carbon monoxide is 0.5-10; the hydrogenation reactor is at least one selected from a slurry bed reactor, a fluidized bed reactor and a fixed bed reactor.
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