CN112569984B - Supported theta iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method - Google Patents

Supported theta iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method Download PDF

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CN112569984B
CN112569984B CN202011059160.5A CN202011059160A CN112569984B CN 112569984 B CN112569984 B CN 112569984B CN 202011059160 A CN202011059160 A CN 202011059160A CN 112569984 B CN112569984 B CN 112569984B
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iron
carbide
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theta
iron carbide
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CN112569984A (en
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王鹏
常海
吕毅军
蒋复国
张琪
门卓武
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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China Energy Investment Corp Ltd
National Institute of Clean and Low Carbon Energy
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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
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J35/613—
    • B01J35/615—
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
    • C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
    • C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group

Abstract

The invention relates to the field of Fischer-Tropsch synthesis reaction, and discloses a supported theta iron carbide-containing composition, a preparation method thereof, a catalyst and application thereof, and a Fischer-Tropsch synthesis method. A supported theta iron carbide-containing composition comprising, based on the total amount of the composition, 55-90 wt% of a carrier and 10-45 wt% of an iron component, wherein the iron component comprises, based on the total amount of the iron component, 95-100mol% of theta iron carbide and 0-5mol% of Fe-containing impurities, which are iron-containing elemental species other than iron carbide. The theta iron carbide can be simply and conveniently prepared, and is used as an active component to obtain continuous and stable Fischer-Tropsch synthesis reaction, and the effective product has high selectivity.

Description

Supported theta iron carbide-containing composition, preparation method thereof, catalyst and application thereof, and Fischer-Tropsch synthesis method
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis reaction, in particular to a supported theta iron carbide-containing composition, a preparation method thereof, a catalyst and application thereof, and a Fischer-Tropsch synthesis method.
Background
The primary energy structure of China is characterized by rich coal, oil deficiency and less gas. With the development of the economy in China, the dependence of petroleum on the outside is continuously increased.
Fischer-Tropsch synthesis is an increasingly important energy conversion pathway in recent years, which can convert carbon monoxide and H 2 Is converted into liquid fuel and chemicals.
The reaction equation for Fischer-Tropsch synthesis is as follows:
(2n+1)H 2 +nCO→C n H 2n+2 +nH 2 O (1)，
2nH 2 +nCO→C n H 2n +nH 2 O (2)。
in addition to alkanes and alkenes, industrial Fischer-Tropsch synthesis can also produce carbon dioxide (CO) 2 ) And methane (CH) 4 ). The Fischer-Tropsch synthesis reaction is complicated in mechanism and numerous in steps, such as CO dissociation, carbon (C) hydrogenation, CH x Chain growth, and hydrogenation and dehydrogenation reactions that result in desorption and oxygen (O) removal of hydrocarbon products.
Iron is the cheapest transition metal for making fischer-tropsch catalysts. Conventional iron-based catalysts have a very high water gas shift (co+h) 2 O→CO 2 +H 2 ) The activity is high, so that the traditional iron-based catalyst usually has higher byproduct CO 2 The selectivity is typically 25% -45% of the carbon monoxide of the conversion feedstock. This is one of the major disadvantages of iron-based catalysts for fischer-tropsch synthesis reactions.
The change of the active phase of the iron-based catalyst is very complex, which results in considerable controversy over the nature of the active phase and the fischer-tropsch reaction mechanism of the iron-based catalyst.
CN104399501A discloses epsilon-Fe suitable for low temperature Fischer-Tropsch synthesis reaction 2 C, a nanoparticle preparation method. The initial precursor is skeleton iron, and the reaction system is intermittent discontinuous reaction of polyglycol solvent. Such a kind of CO of catalyst 2 Selectivity is 18.9%, CH 4 The selectivity bit of (2) 17.3%. The disadvantage is that the reaction can not be continuously completed only when the reaction is applied to low temperatures below 200 ℃. This means that such catalysts are not suitable for continuous production under modern fischer-tropsch synthesis industry conditions. (however, since the skeleton iron cannot be completely carbonized, ε -Fe described in the publication 2 C contains a considerable amount of non-iron carbide type iron impurity components in the nano-particles, and in fact, the prior art cannot obtain pure-phase iron carbide materials free of iron impurities, where Fe impurities refer to various Fe (elemental) containing phase components other than iron carbide.
Therefore, improvements in iron-based catalysts used in fischer-tropsch synthesis reactions are needed.
Disclosure of Invention
The invention aims to solve the problem of how to obtain pure-phase iron carbide substances without Fe impurities by an iron-based catalyst, improve the stability of Fischer-Tropsch synthesis reaction and reduce CO at the same time 2 Or CH (CH) 4 The problem of excessive selectivity of byproducts is solved, and the composition containing the supported theta iron carbide, the preparation method, the catalyst and the application thereof and the Fischer-Tropsch synthesis method are provided.
In order to achieve the above object, the first aspect of the present invention provides a supported theta iron carbide-containing composition comprising 55 to 90 wt% of a carrier and 10 to 45 wt% of an iron component, based on the total amount of the composition, wherein the iron component comprises 95 to 100mol% of theta iron carbide and 0 to 5mol% of Fe-containing impurities, which are iron-containing substances other than theta iron carbide, based on the total amount of the iron component.
In a second aspect, the invention provides a method of preparing a supported θ -iron carbide-containing composition comprising:
(1) Impregnating the carrier in an aqueous solution of ferric salt, and drying and roasting the impregnated carrier to obtain a precursor;
(2) Combining the precursor with H 2 At temperature T 1 Precursor reduction is carried out at 340-600 ℃;
(3) Mixing the material obtained in the step (2) with H 2 CO at temperature T 2 Carbonization is carried out at 280-420 DEG CPreparing the material for 20-120H, wherein H 2 The mol ratio of CO to CO is 5-120:1, obtaining load type theta iron carbide;
(4) Mixing the supported theta iron carbide with Fe-containing impurities under the protection of inert gas;
wherein the amount of the supported theta iron carbide and the amount of the Fe-containing impurities are such that the resulting composition comprises 55 to 90 wt% of the carrier and 10 to 45 wt% of the iron component, based on the total amount of the composition; the iron component comprises 95-100mol% of theta iron carbide and 0-5mol% of Fe-containing impurities, based on the total amount of the iron component;
wherein the Fe-containing impurities are iron-containing substances other than theta iron carbide.
The third aspect of the invention provides a supported theta iron carbide-containing composition prepared by the method provided by the invention.
In a fourth aspect, the present invention provides a catalyst comprising the supported θ -iron carbide-containing composition provided herein.
In a fifth aspect, the invention provides the use of the supported θ iron carbide containing composition or catalyst provided by the invention in a fischer-tropsch synthesis reaction.
In a sixth aspect, the present invention provides the use of a supported theta iron carbide containing composition or catalyst according to the present invention for the synthesis of C, H fuels and/or chemicals based on the fischer-tropsch synthesis principle.
In a seventh aspect the invention provides a method of fischer-tropsch synthesis comprising: under the Fischer-Tropsch reaction conditions, the synthesis gas is contacted with the supported theta iron carbide containing composition or catalyst provided by the invention.
In an eighth aspect the invention provides a method of fischer-tropsch synthesis comprising: the synthesis gas is contacted with a Fischer-Tropsch catalyst under Fischer-Tropsch reaction conditions, wherein the Fischer-Tropsch catalyst comprises a Mn component and the supported theta iron carbide containing composition provided by the invention.
Through the technical scheme, the invention has the following technical effects:
(1) The required raw materials are simple and easy to obtain, and the cost is low: the main raw material iron source of the synthesis precursor can be commercial ferric salt, and when active phase carbide is synthesized, only the original reaction gas (carbon monoxide and hydrogen) of a Fischer-Tropsch synthesis reaction system is utilized, no inorganic or organic matter reflection raw material is involved, and compared with the prior literature technology, the method is greatly simplified;
(2) The operation steps are simple, and in the preferred embodiment, the whole process for preparing the supported theta iron carbide only needs two steps of precursor reduction and carbide preparation, so that the preparation of an active phase can be realized in situ in the same reactor;
(3) The method comprises the steps of preparing 100% purity active phase theta iron carbide loaded on a carrier, and then forming a composition with Fe-containing impurities to further prepare the catalyst. The iron carbide or the composition or the catalyst can be used in a high-temperature and high-pressure (for example, the temperature of 265-350 ℃ and the pressure of 1.5-3.5 MPa) continuous reactor, has extremely high reaction stability, breaks through the theoretical technical barrier of the traditional literature theory that pure iron carbide cannot exist stably under the reaction condition, can realize the stable temperature of 350 ℃ and CO 2 The selectivity is extremely low: under the condition of industrial Fischer-Tropsch synthesis reaction, a high-pressure continuous reactor can be used for maintaining continuous stable reaction for more than 400 hours, and CO thereof 2 The selectivity is below 12% (preferably below 6%; at the same time, its by-product CH 4 The selectivity is kept at 14 percent (under the preferential condition, the selectivity can reach below 7 percent), the selectivity of the effective product can reach above 74 percent (under the preferential condition, the selectivity can reach above 85 percent), and the method is very suitable for the high-efficiency oil wax production product in the modern coal industry Fischer-Tropsch synthesis industry.
Drawings
FIG. 1 is an in situ XRD spectrum of a process for preparing supported θ iron carbide in example 1 provided herein; wherein, before the reduction of the A-precursor, after the reduction of the B-precursor, the preparation of the C-iron carbide is completed.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the present invention provides a supported theta iron carbide-containing composition comprising, based on the total amount of the composition, 55 to 90 wt% of a carrier and 10 to 45 wt% of an iron component, wherein the iron component comprises, based on the total amount of the iron component, 95 to 100mol% of theta iron carbide and 0 to 5mol% of an Fe-containing impurity, the Fe-containing impurity being an elemental iron-containing substance other than theta iron carbide.
The supported type theta iron carbide-containing composition provided by the invention comprises theta iron carbide with the purity of 100%. Further, the supported θ iron carbide may be combined with other Fe-containing impurities to form a composition. Under the limitation of the content, when the supported theta iron carbide-containing composition provided by the invention can be applied to a Fischer-Tropsch synthesis catalyst, the composition can be singly used or is distributed with other components, so that the stability of the Fischer-Tropsch synthesis catalyst in the Fischer-Tropsch synthesis reaction can be improved, and the CO is greatly reduced 2 Or CH (CH) 4 By-product selectivity.
In some embodiments of the invention, the compositions comprise high purity supported theta iron carbide, and XRD and mussburgh spectral analysis is performed to observe that the crystalline phase comprises pure theta iron carbide on the obtained XRD and mussburgh spectral results. Preferably, the specific surface area of the composition is 40-500m 2 Preferably 45-350m 2 And/g. The specific surface area can be determined by N 2 Is determined by BET adsorption and desorption methods. The composition is orthorhombic theta iron carbide.
In some embodiments of the invention, it is further preferred that the composition comprises 60-85 wt% carrier and 15-40 wt% iron component, based on the total amount of the composition. Can be determined by elemental analysis. The support may be selected from at least one of silica, alumina, titania, niobium pentoxide and zirconia.
In some embodiments of the present invention, it is further preferred that the iron component comprises 97 to 100mol% of theta iron carbide and 0 to 3mol% of Fe-containing impurities, based on the total amount of the iron component. Can be determined by XRD and Mossburg spectrometry analysis, and can also be determined according to the preparation feeding amount of the composition.
In some embodiments of the invention, the Fe-containing impurity is at least one of iron carbide other than theta iron carbide, iron oxide, iron hydroxide, iron sulfide, iron salt. The Fe-containing impurities may be introduced by solution impregnation, sputtering, atomic deposition or mixing.
In a second aspect, the invention provides a method of preparing a composition comprising supported θ iron carbide, comprising:
(1) Impregnating the carrier in an aqueous solution of ferric salt, and drying and roasting the impregnated carrier to obtain a precursor;
(2) Combining the precursor with H 2 At temperature T 1 Precursor reduction is carried out at 340-600 ℃;
(3) Mixing the material obtained in the step (2) with H 2 CO at temperature T 2 Carbide preparation is carried out at 280-420 ℃ for 20-120H, wherein H 2 The mol ratio of CO to CO is 5-120:1, obtaining load type theta iron carbide;
(4) Mixing the supported theta iron carbide with Fe-containing impurities under the protection of inert gas;
wherein the amount of the supported theta iron carbide and the amount of the Fe-containing impurities are such that the resulting composition comprises 55 to 90 wt% of the carrier and 10 to 45 wt% of the iron component, based on the total amount of the composition; the iron component comprises 95-100mol% of theta iron carbide and 0-5mol% of Fe-containing impurities, based on the total amount of the iron component;
wherein the Fe-containing impurities are iron-containing substances other than theta iron carbide.
In some embodiments of the present invention, the iron salt may be a water-soluble iron salt commonly used in the art, the iron salt is selected from water-soluble iron salts, and may be commercially available, for example, the iron salt is at least one of ferric nitrate, ferric chloride, ferrous ammonium sulfate, and ferric ammonium citrate.
In some embodiments of the invention, the support may be a conventional choice in the art, for example, the catalyst support is at least one of silica, alumina, titania, niobium pentoxide, and zirconia. In the present invention, it is preferable that the particle size of the carrier is 30 to 200. Mu.m.
In some embodiments of the invention, preferably, the impregnation is such that the iron content of the impregnated support after drying is from 10 to 30% by weight. The impregnation may be a conventional choice in the art as long as it enables the loading of iron in the impregnated support to be achieved, preferably the impregnation is a saturated impregnation process.
In a preferred embodiment of the present invention, the drying and roasting process includes: firstly, drying the impregnated carrier for 0.5-4h at 20-30 ℃, then drying for 6-10h at 35-80 ℃ and a vacuum degree of 250-1200Pa, drying the dried material for 3-24h at 110-150 ℃, and roasting the obtained material for 1-10h at 300-550 ℃. The drying process can be performed in an oven, and the roasting process can be performed in a muffle furnace.
In some embodiments of the present invention, the step (2) may simultaneously perform the function of generating nano iron powder in situ from the iron element in the precursor and reducing the generated nano iron powder.
In some embodiments of the invention, H in step (2) 2 Can be H 2 The flow is introduced into the reaction system and at the same time, H is controlled 2 The pressure of the stream controls the pressure of the precursor reduction, preferably in step (1), the precursor is also at a pressure of 0.1-15atm, preferably 0.3-2.6atm, for a time of 0.7-15h, preferably 1-12h.
In some embodiments of the invention, H 2 The amount of (2) may be selected according to the amount of the raw material to be treated, preferably H 2 The gas flow rate of (C) is 600-25000mL/h/g, more preferably 2800-22000mL/h/g.
In step (3) of the method provided by the invention, conditions are provided for achieving the carbide preparation to obtain the supported θ iron carbide. H 2 And CO can be (H) 2 +co) in the form of a mixed gas stream into the process for the preparation of said carbide; at the same time, by controlling (H 2 +co) pressure of the mixed gas stream to control the pressure of the carbide manufacturing process. Preferably, in step (3), the carbide is produced at a pressure of 0 to 28atm, preferably0.01-20atm for 20-120 hours, preferably 24-80 hours.
In some embodiments of the present invention, preferably, in step (3), H 2 The total gas flow rate with CO is 200-35000mL/h/g, more preferably 1200-20000mL/h/g.
In a preferred embodiment of the present invention, the carbide preparation further comprises: in the step (3), the temperature changing operation is also carried out at the same time, and the temperature is changed from the temperature T 1 Cooling or heating to temperature T at a variable temperature rate of 0.2-5deg.C/min 2 . In this preferred embodiment, the resulting supported θiron carbide may have better effective product selectivity in the fischer-tropsch reaction. Further preferably, from temperature T 1 The temperature is reduced or increased to 300-400 ℃ at a variable temperature rate of 0.2-2.5 ℃/min.
In the present invention, "mL/h/g" refers to the volume of air intake per gram of material per hour during the iron carbide production process, unless otherwise specified.
In another preferred embodiment of the invention, the precursor reduction and carbide preparation process is more simple to operate in a Fischer-Tropsch synthesis reactor. In-situ characterization equipment can be used for tracking the crystal phase transition of materials in the preparation process.
In some embodiments of the invention, obtaining a loaded θ iron carbide can be achieved by the process of steps (1) through (3). Can be determined by XRD and/or musburg spectroscopy.
In some embodiments of the present invention, the Fe-containing impurities contained in the supported θ iron carbide-containing composition may be mixed by an external means. Preferably, it comprises 60-85 wt% of carrier and 15-40 wt% of iron component, based on the total amount of the composition; the iron component comprises 97-100mol% pure theta iron carbide and 0-3mol% Fe-containing impurities, based on the total amount of the iron component.
In the step (4) of the method provided by the invention, the powder of the supported theta iron carbide and the powder containing Fe impurities are mixed according to the dosage requirement in a glove box under the protection of inert gas.
In a third aspect, the invention provides a θ -containing iron carbide composition made by the method of the invention. The composition comprises 55-90 wt% of a carrier and 10-45 wt% of an iron component, based on the total amount of the composition, wherein the iron component comprises 95-100mol% of theta iron carbide and 0-5mol% of Fe-containing impurities, based on the total amount of the iron component, which are iron-containing substances other than theta iron carbide.
Preferably, the composition comprises 60-85 wt% carrier and 15-40 wt% iron component, based on the total amount of the composition; the iron component comprises 97-100mol% of theta iron carbide and 0-3mol% of Fe-containing impurities, based on the total amount of the iron component.
Preferably, the specific surface area of the composition is 40-500m 2 Preferably 45-350m 2 /g。
In a fourth aspect, the present invention provides a catalyst comprising the supported θ -iron carbide-containing composition provided herein. Preferably, the catalyst may also comprise other components, such as adjuvants.
In the specific embodiment provided by the invention, preferably, the content of the supported theta iron carbide-containing composition is more than 75wt% and less than 100wt%, and the content of the auxiliary agent is more than 0wt% and less than 25wt%, based on the total amount of the catalyst.
In the specific embodiment provided by the invention, the catalyst can be prepared by introducing the auxiliary agent by a dipping, atomic deposition, sputtering or chemical deposition method.
In a fifth aspect, the invention provides the use of a composition or catalyst comprising θ iron carbide as provided herein in a fischer-tropsch synthesis reaction.
In a sixth aspect, the invention provides the use of a composition or catalyst comprising iron theta carbide as provided herein in a synthesis reaction of C, H fuel and/or chemicals based on the fischer-tropsch principle.
In a seventh aspect the invention provides a method of fischer-tropsch synthesis comprising: the synthesis gas is contacted with the theta iron carbide containing composition or catalyst provided by the present invention under fischer-tropsch reaction conditions.
The supported theta iron carbide-containing composition of the inventionOr the catalyst, may be subjected to a fischer-tropsch synthesis reaction which can be carried out at elevated temperature and pressure, for example, the conditions of the fischer-tropsch synthesis reaction include: the temperature is 265-350 ℃ and the pressure is 1.5-3.5MPa. But also can be particularly better in the selectivity of effective products; the effective products are CO and H 2 Generated by reaction, except CH 4 With CO 2 Other carbon-containing products, including, but not limited to, C 2 C 2 The above hydrocarbons, alcohols, aldehydes, ketones, esters, and the like.
In the present invention, unless otherwise specified, the pressure refers to gauge pressure.
In some embodiments of the invention, preferably, the Fischer-Tropsch synthesis reaction is carried out in a high temperature, high pressure continuous reactor. The composition or the catalyst containing the theta iron carbide can realize that the Fischer-Tropsch synthesis reaction keeps continuous stable reaction for more than 400 hours in a high-temperature high-pressure continuous reactor.
In an eighth aspect the invention provides a method of fischer-tropsch synthesis comprising: the synthesis gas is contacted with a Fischer-Tropsch catalyst under Fischer-Tropsch reaction conditions, wherein the Fischer-Tropsch catalyst comprises a Mn component and the θ -containing iron carbide composition provided herein.
In the specific embodiment provided by the invention, the composition of the Fischer-Tropsch catalyst can be further based on the total amount of the Fischer-Tropsch catalyst, the content of the supported theta iron carbide-containing composition is more than 75wt% and less than 100wt%, and the content of Mn is more than 0wt% and less than 25 wt%. In the fischer-tropsch catalyst, mn may be present in the form of oxides and may be introduced into the fischer-tropsch catalyst by methods including, but not limited to, impregnation, chemical deposition, sputtering, atomic deposition.
The present invention will be described in detail by examples. In the following examples and comparative examples,
in-situ XRD detection during the preparation of the iron carbide is carried out by using an X-ray diffractometer (Rigaku company, model D/max-2600/PC) to monitor the crystal phase change of the material;
the obtained iron carbide and iron carbide composition is subjected to Mossburger spectrometer (Transmission 57 Fe， 57 Co (Rh) source sineVelocity spectrometer) to perform musburger spectrum detection;
the BET specific surface area of the iron carbide composition is determined by nitrogen adsorption;
in the Fischer-Tropsch synthesis:
carrying out gas chromatographic analysis (Agilent 6890 gas chromatography) on the product obtained by the reaction;
the reaction effect is calculated by the following formula:
CO 2 selectivity% 2 Mole/(mole of CO in feed-mole of CO in discharge)]×100％；
CH 4 Selectivity = [ CH in discharge ] 4 Mole number/(mole number of CO in feed X CO conversion (1-CO) 2 Selectivity%))]×100％；
Effective product selectivity% = [1-CO 2 Selectivity% -CH 4 Selectivity%]×100％
Feed CO space time conversion rate (mmol/h/g) -Fe ) = (moles of CO in feed-moles of CO in discharge)/reaction time/weight of Fe element;
space-time yield of the effective product formation (mmol/h/g) -Fe ) C of =reaction 2 C (C) 2 The above hydrocarbon mole number/reaction time/Fe element weight.
Example 1
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 30wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 2.6atm, H 2 22000mL/h/g, and reducing the precursor for 12h at the temperature of 450 ℃;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 400 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And COThe mixed gas is contacted to prepare the load type carbide, and the conditions are as follows: pressure 20atm, total gas flow 20000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 24 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 1;
(4) Under the protection of Ar gas, 97 mole parts of supported iron carbide 1 and 3 mole parts of ferrous oxide (namely Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 1.
Example 2
(1) 20g of titanium oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 10wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 0.3atm, H 2 2800mL/h/g, and reducing the precursor for 1h at 450 ℃;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 300 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 0.01atm, total gas flow 1200mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 80 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 2;
(4) 97 mole parts of supported iron carbide 2 and 3 mole parts of ferrous oxide (i.e., fe-containing impurities) are mixed under Ar gas protection. The mixture was designated as supported iron carbide composition 2.
Example 3
(1) 20g of alumina is weighed as a carrier, and then impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 3;
(4) Under the protection of Ar gas, 99 mole parts of supported iron carbide 3 and 1 mole part of ferrous oxide (namely Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 3.
Example 4
(1) - (3) following the procedure of example 1, except that in step (2), "precursor with H 2 At a pressure of 3atm ", the precursor is replaced with H 2 The supported iron carbide was obtained at a pressure of 2.6atm ", and the supported iron was measured by musburg spectroscopy to be pure θ iron carbide, which was designated as supported iron carbide 4.
(4) Under the protection of Ar gas, 98 mole parts of supported iron carbide 4 and 2 mole parts of ferrous oxide (namely Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 4.
Example 5
(1) - (3) following the procedure of example 1, except that in step (2), "precursor with H 2 At a pressure of 0.08atm ", the" precursor and H "are replaced 2 The supported iron carbide was obtained at a pressure of 2.6atm ", and the supported iron was measured by musburg spectroscopy to be pure θ iron carbide, which was designated as supported iron carbide 5.
(4) 97 mole parts of supported iron carbide 5 and 3 mole parts of ferrous oxide (i.e., fe-containing impurities) were mixed under Ar gas protection. The mixture was designated as supported iron carbide composition 5.
Example 6
(1) 20g of niobium pentoxide is weighed as a carrier, and then impregnation is carried out by using an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of the simple substance iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 13h at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 3;
(4) Under the protection of Ar gas, 98 mole parts of supported iron carbide 6 and 2 mole parts of ferrous oxide (namely Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 6.
Example 7
(1) 20g of niobium pentoxide is weighed as a carrier, and then impregnation is carried out by using an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of the simple substance iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 Is introduced at a temperature of 450 ℃ at a flow rate of 10000mL/h/gReducing the precursor for 0.5h;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 7;
(4) Under the protection of Ar gas, 99 mole parts of supported iron carbide 7 and 1 mole part of ferrous oxide (namely Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 7.
Example 8
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 23000mL/h/g, and reducing the precursor at 450 ℃ for 6h;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 8;
(4) Under the protection of Ar gas, 99 mole parts of supported iron carbide 8 and 1 mole part of ferrous oxide (namely Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 8.
Example 9
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The flow rate of the catalyst is 500mL/h/g, and precursor reduction is carried out for 10h at the temperature of 450 ℃;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 9;
(4) Under the protection of Ar gas, 98 mole parts of supported iron carbide 9 and 2 mole parts of ferrous oxide (namely Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 9.
Example 10
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 410 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 Contact with CO gas mixtureThe preparation of the supported carbide is carried out under the following conditions: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 10;
(4) 97 mole parts of the supported iron carbide 10 and 3 mole parts of ferrous oxide (i.e., fe-containing impurities) were mixed under Ar gas protection. After mixing, this is designated as supported iron carbide composition 10.
Example 11
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in step (2) from 450 ℃ to 270 ℃ at a rate of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 11;
(4) Under the protection of Ar gas, 99 mole parts of supported iron carbide 11 and 1 mole part of ferrous oxide (i.e. Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 11.
Example 12
(1) 20g of zirconia was weighed as a carrier and then impregnated with an aqueous solution of ferric ammonium citrate, which was weighed and prepared at a content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 85 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 12;
(4) 99 mole parts of the supported iron carbide 12 are mixed with 1 mole part of ferrous oxide (i.e., fe-containing impurities) under Ar gas protection. After mixing, this is designated as supported iron carbide composition 12.
Example 13
(1) 20g of zirconia was weighed as a carrier and then impregnated with an aqueous solution of ferric ammonium citrate, which was weighed and prepared at a content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron carbide to CO is 60:1, the treatment time is 18 hours, the loaded iron carbide is obtained, and the iron carbide is subjected to Mossburger reactionThe iron loaded by the spectrum measurement is pure theta iron carbide and is marked as loaded iron carbide 13;
(4) Under the protection of Ar gas, 98 mole parts of supported iron carbide 13 and 2 mole parts of ferrous oxide (i.e., fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition 13.
Example 14
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 22atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 14;
(4) 99 mole parts of the supported iron carbide 14 were mixed with 1 mole part of ferrous oxide (i.e., fe-containing impurities) under Ar gas protection. After mixing, this is denoted as supported iron carbide composition 14.
Example 15
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 0.005atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 15;
(4) Under the protection of Ar gas, 98 mole parts of supported iron carbide 15 and 2 mole parts of ferrous oxide (i.e., fe-containing impurities) are mixed. After mixing, this was designated as supported iron carbide composition 15.
Example 16
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 22000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 16;
(4) 97 mole parts of the supported iron carbide 16 and 3 mole parts of ferrous oxide (i.e., fe-containing impurities) were mixed under Ar gas protection. After mixing, this is designated as supported iron carbide composition 16.
Example 17
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 150mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 17;
(4) 99 mole parts of the supported iron carbide 17 were mixed with 1 mole part of ferrous oxide (i.e., fe-containing impurities) under Ar gas protection. After mixing, this was designated as supported iron carbide composition 17.
Example 18
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 10000mL/h/g, at a temperature of 450 DEG CReducing the precursor for 6h;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a rate of 3 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 18;
(4) Under the protection of Ar gas, 98 mole parts of the supported iron carbide 18 and 2 mole parts of ferrous oxide (i.e., fe-containing impurities) were mixed. After mixing, this is denoted as supported iron carbide composition 18.
Example 19
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a rate of 0.1 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron to CO is 60:1, the treatment time is 48 hours, the loaded iron is obtained, and the iron which is loaded by Mossburg spectroscopy is pure theta iron carbide and is recorded as loaded iron carbide 19;
(4) 97 mole parts of the supported iron carbide 19 were mixed with 3 mole parts of ferrous oxide (i.e., fe-containing impurities) under Ar gas protection. After mixing, this was designated as supported iron carbide composition 19.
Comparative example 1
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at 620 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in step (2) from 620 ℃ to 350 ℃ at a rate of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron carbide to CO is 60:1, the treatment time is 48 hours, and the loaded iron carbide is obtained and is marked as loaded iron carbide D1;
(4) Under the protection of Ar gas, 99 mole parts of supported iron carbide D1 and 1 mole part of ferrous oxide (namely Fe-containing impurities) are mixed. The mixture was designated as supported iron carbide composition D1.
Comparative example 2
(1) 20g of silicon oxide is weighed as a carrier, and then is impregnated with an aqueous solution of ferric ammonium citrate, wherein the aqueous solution of ferric ammonium citrate is weighed and prepared according to the content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at 320 ℃ at the flow rate of 10000 mL/h/g;
(3) Heating the product obtained in the step (2) from 320 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure of 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron carbide to CO is 60:1, the treatment time is 48 hours, and the loaded iron carbide is obtained and is marked as loaded iron carbide D2;
(4) Under the protection of Ar gas, 99 mole parts of supported iron carbide D2 and 1 mole part of ferrous oxide (namely Fe-containing impurities) are mixed. After mixing, the mixture was designated as supported iron carbide composition D2.
Comparative example 3
(1) 20g of zirconia was weighed as a carrier and then impregnated with an aqueous solution of ferric ammonium citrate, which was weighed and prepared at a content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron carbide to CO is 130:1, the treatment time is 48 hours, and the loaded iron carbide is obtained and is marked as loaded iron carbide D3;
(4) Under the protection of Ar gas, 99 mole parts of supported iron carbide D3 and 1 mole part of ferrous oxide (namely Fe-containing impurities) are mixed. After mixing, this was designated as supported iron carbide composition D3.
Comparative example 4
(1) 20g of zirconia was weighed as a carrier and then impregnated with an aqueous solution of ferric ammonium citrate, which was weighed and prepared at a content of 25wt% of elemental iron in the final carrier. Drying the impregnated carrier at 30 ℃ for 2 hours, then drying the carrier in a vacuum drying oven at 40 ℃ and a vacuum degree of 300Pa for 8 hours, drying the dried material at 120 ℃ for 24 hours in an oven, and roasting the obtained material at 500 ℃ for 5 hours in a muffle furnace. Obtaining a load type iron-based precursor;
(2) Precursor and H 2 At a pressure of 1.5atm, H 2 The precursor is reduced for 6 hours at the temperature of 450 ℃ at the flow rate of 10000 mL/h/g;
(3) Cooling the product obtained in the step (2) from 450 ℃ to 350 ℃ at a speed of 1.5 ℃/min, and reacting with H at the temperature 2 And (3) carrying out preparation of the supported carbide by contacting with CO mixed gas, wherein the conditions are as follows: pressure 10atm, total gas flow 10000mL/H/g, H 2 The molar ratio of the iron carbide to CO is 3:1, the treatment time is 48 hours, and the loaded iron carbide is obtained and is marked as loaded iron carbide D4;
(4) Under the protection of Ar gas, 99 mole parts of supported iron carbide D4 and 1 mole part of ferrous oxide (namely Fe-containing impurities) are mixed. After mixing, the mixture was designated as supported iron carbide composition D4.
Comparative example 5
According to the method of example 1, except that (4) 91 parts by mole of the supported iron carbide 1 and 9 parts by mole of the ferrous oxide (i.e., fe-containing impurity) were mixed under Ar gas. After mixing, this was designated as supported iron carbide composition D5.
Examples 20 to 38
Respectively taking supported iron carbide compositions 1-19, and adding N 2 Under protection, respectively adding manganese citrate solution by impregnation method, and adding N at 25deg.C 2 And drying the air flow for 24 hours to obtain the Fischer-Tropsch catalyst 1-19. Wherein the amount of the manganese citrate solution added by impregnation is such that the resulting Fischer-Tropsch catalysts 1-19 respectively contain 85wt% of the supported iron carbide composition 1-19, 15wt% of MnO 2 。
Comparative examples 6 to 10
The supported iron carbide compositions D1-D5 were taken separately, at N 2 Under protection, respectively adding manganese citrate solution by impregnation method, and adding N at 25deg.C 2 And drying the air flow for 24 hours to obtain the Fischer-Tropsch catalysts D1-D5 correspondingly. Wherein the amount of manganese citrate solution added by impregnation is such that the resulting Fischer-Tropsch catalysts D1-D5 respectively contain 85wt% of the supported iron carbide composition D1-D5, 15wt% of MnO 2 。
Test case
Mossburger spectrum measurement is carried out on the iron carbide 1-19 and the iron carbide D1-D4, and the content result of the measured Fe compound is shown in Table 1. Wherein the content unit of Fe compound is mole percent.
TABLE 1
Iron carbide numbering Theta iron carbide content (mol%) Content of other Fe-containing impurities (mol%)
1-24 100.0 0.0
D1 54.0 46.0
D2 41.0 59.0
D3 38.0 62.0
D4 40.0 60.0
Wherein the whole process of preparing the iron carbide 1 of example 1 adopts an in-situ XRD detection technique using an X-ray diffractometer (Rigaku Co., ltd.)No. D/max-2600/PC) to monitor the change of crystal phase of the material. As shown in fig. 1, curve a is before the precursor reduction in step (1), B is after the precursor reduction, and C is after the carbide preparation is completed. Wherein curve A is alpha-Fe 2 O 3 The characteristic peaks 2θ=33.3°, 35.7 °, 41.0 °, 49.5 °, 54.2 °, 57.6 °, 62.7 ° and the like are completely consistent with the standard card PDF-02-0919. B is an α -Fe crystalline phase, and its characteristic peaks 2θ=44.7 °, 65.0 °, 82.3 °, are consistent with the XRD standard card PDF-65-4899 of α -Fe. Curve C is the orthorhombic system theta-Fe with 100% purity 3 C, i.e., theta iron carbide, which exhibits 2 theta main peaks=36.6 °, 37.8 °, 42.9 °, 43.8 °, 44.6 °, 45.0 °, 45.9 °, 48.6 °, 49.1 ° all characteristic peaks with theta-Fe 3 The C standard card PDF-65-2142 is completely consistent. The obtained spectrogram can clearly see the change process from nano iron powder to target carbide. The crystallization degree of the generated target product theta iron carbide is good, all characteristic peaks of the theta iron carbide are well corresponding, the purity is extremely high, and no other impurities exist.
Mossburg spectra and BET specific surface areas were measured for iron carbide compositions 1-24 and D1-D7, respectively, and the results are shown in Table 2.
TABLE 2
Figure BDA0002711731530000251
Evaluation example
Catalytic performance evaluations were performed on Fischer-Tropsch catalysts 1-24, D1-D7, and iron carbide compositions 1-3, respectively, in a fixed bed continuous reactor. The catalyst loading was 10.0g.
Evaluation conditions: t=315 ℃, p=2.35 mpa, h 2 ：CO＝1.9：1，(H 2 +co) total = 55000mL/h/g- Fe (standard state flow, relative to the Fe element). The reaction was carried out and the reaction products were analyzed by gas chromatography, and evaluation data of the reactions for 24 hours and 400 hours are shown in tables 3 and 4.
TABLE 3 Table 3
Figure BDA0002711731530000252
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Figure BDA0002711731530000261
TABLE 4 Table 4
Figure BDA0002711731530000262
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Figure BDA0002711731530000271
As can be seen from the above examples, comparative examples and the data in tables 1-4, the supported theta iron carbide or composition or catalyst prepared according to the present invention is subjected to Fischer-Tropsch synthesis under industrial conditions, and exhibits high space-time conversion rate of raw material CO, better reactivity, and ultra-low CO within a limited range of conditions 2 Selectivity. At the same time CH 4 The selectivity is low, and the selectivity of effective products is high.
Further carrying out long-period experiments, the data of the reaction for 400h in the table 4 show that after the supported theta iron carbide-containing composition or the catalyst prepared under the limiting conditions provided by the invention is operated for a long time, the CO conversion rate and the product selectivity are stable, no obvious change exists, and the stability is greatly superior to that of the iron carbide in the prior art.
The supported theta iron carbide or the composition or the catalyst prepared under the limiting condition of the invention can be suitable for a high-temperature high-pressure continuous reactor, has high reaction stability and CO 2 The selectivity is extremely low: under the condition of industrial Fischer-Tropsch synthesis reaction, a high-pressure continuous reactor can be used for maintaining continuous stable reaction for more than 400 hours, and CO thereof 2 The selectivity is below 12% (preferably 6% or below); at the same time, its by-product CH 4 The selectivity is kept below 14% (preferably below 7%) and the selectivity of the effective product is above 74% (preferably above 87%). Wherein the preferred conditions are such that the catalyst is effective in the formation of the productThe space yield can reach 255mmol/h/g- Fe The method is very suitable for efficiently producing oil and wax products in the large industrial of the Fischer-Tropsch synthesis of the modern coal industry.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of individual specific technical features in any suitable way. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition. Such simple variations and combinations are likewise to be regarded as being within the scope of the present disclosure.

Claims (19)

1. A method of preparing a supported theta iron carbide containing composition comprising:
(1) Impregnating the carrier in an aqueous solution of ferric salt, and drying and roasting the impregnated carrier to obtain a precursor;
(2) Combining the precursor with H 2 At temperature T 1 Precursor reduction is carried out at 340-600 ℃;
(3) Mixing the material obtained in the step (2) with H 2 CO at temperature T 2 Carbide preparation is carried out at 280-420 ℃ for 20-120H, wherein H 2 The mol ratio of CO to CO is 5-120:1, obtaining load type theta iron carbide;
(4) Mixing the supported theta iron carbide with Fe-containing impurities under the protection of inert gas;
wherein the amount of the supported theta iron carbide and the amount of the Fe-containing impurities are such that the resulting composition comprises 55 to 90 wt% of the carrier and 10 to 45 wt% of the iron component, based on the total amount of the composition; the iron component comprises 95-100mol% of theta iron carbide and 0-5mol% of Fe-containing impurities, based on the total amount of the iron component; the Fe-containing impurity is not 0;
Wherein the Fe-containing impurities are iron-containing substances other than theta iron carbide.
2. The method according to claim 1The method, wherein the specific surface area of the composition is 40-500m 2 /g。
3. The method according to claim 2, wherein the specific surface area of the composition is 45-300m 2 /g。
4. The method of claim 1, wherein the Fe-containing impurity is at least one of iron carbide other than θiron carbide, iron oxide, iron hydroxide, iron sulfide, iron salt.
5. The method of claim 1, wherein the iron salt is selected from water-soluble iron salts;
and/or, the impregnation is such that the iron content in the dried impregnated support is 10-30 wt.%;
and/or, the drying and roasting processes comprise: firstly, drying the impregnated carrier for 0.5-4h at 20-30 ℃, then drying for 6-10h at 35-80 ℃ and a vacuum degree of 250-1200Pa, drying the dried material for 3-24h at 110-150 ℃, and roasting the obtained material for 1-10h at 300-550 ℃.
6. The method of claim 5, wherein the iron salt is selected from at least one of ferric nitrate, ferric chloride, ferrous ammonium sulfate, and ferric ammonium citrate.
7. The method of any one of claims 1-6, wherein the support is at least one of silica, alumina, titania, niobium pentoxide, and zirconia;
and/or the carrier has a particle size of 30-200 μm.
8. The method according to any one of claims 1 to 6, wherein in step (2), the precursor is reduced at a pressure of 0.1 to 15atm for a time of 0.7 to 15 hours;
and/or, in step (2), H 2 The gas flow rate of (2) is 600-25000 mL/h-g。
9. The method of claim 8, wherein in the step (2), the pressure of the precursor reduction is 0.3-2.6atm for 1-12 hours;
and/or, in step (2), H 2 The gas flow rate of (2) is 2800-22000mL/h/g.
10. The method according to any one of claims 1 to 6, wherein in the step (3), the carbide is prepared at a pressure of 0 to 28atm for a time of 20 to 120 hours;
and/or, in step (3), H 2 The total gas flow rate with CO is 200-35000mL/h/g.
11. The method according to claim 10, wherein in the step (3), the carbide is prepared at a pressure of 0.01-20atm for a time of 24-80 hours;
and/or, in step (3), H 2 The total gas flow rate with CO is 1200-20000 mL/h/g.
12. The method of any of claims 1-6, wherein the carbide preparation further comprises: in the step (3), the temperature changing operation is also carried out at the same time, and the temperature is changed from the temperature T 1 Cooling or heating to temperature T at a variable temperature rate of 0.2-5deg.C/min 2 。
13. The method of claim 12, wherein the temperature T is selected from 1 The temperature is reduced or increased to 300-400 ℃ at a variable temperature rate of 0.2-2.5 ℃/min.
14. The method of any of claims 1-6, wherein the carrier comprises 60-85 wt% and 15-40 wt% of the iron component, based on the total amount of the composition;
the iron component comprises 97-100mol% of theta iron carbide and 0-3mol% of Fe-containing impurities, based on the total amount of the iron component.
15. Use of a supported theta iron carbide containing composition made by the process of any one of claims 1 to 14 in a fischer-tropsch synthesis reaction.
16. Use of a catalyst comprising a supported theta iron carbide containing composition produced by the method of any one of claims 1 to 14 in a fischer-tropsch based synthesis reaction of C, H fuels and/or chemicals.
17. A method of fischer-tropsch synthesis comprising: contacting the synthesis gas with the supported iron theta carbide containing composition produced by the process of any one of claims 1 to 14 or a catalyst comprising the supported iron theta carbide containing composition produced by the process of any one of claims 1 to 14 under fischer-tropsch synthesis reaction conditions.
18. The process of claim 17 wherein the fischer-tropsch synthesis is carried out in a high temperature, high pressure continuous reactor.
19. A method of fischer-tropsch synthesis comprising: contacting synthesis gas with a fischer-tropsch catalyst under fischer-tropsch reaction conditions, wherein the fischer-tropsch catalyst comprises a Mn component and the supported theta iron carbide containing composition produced by the process of any of claims 1 to 14.
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