CN117358245B - Red mud-based thermal catalyst with shell-core structure, and preparation method and application thereof - Google Patents

Red mud-based thermal catalyst with shell-core structure, and preparation method and application thereof Download PDF

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CN117358245B
CN117358245B CN202311671235.9A CN202311671235A CN117358245B CN 117358245 B CN117358245 B CN 117358245B CN 202311671235 A CN202311671235 A CN 202311671235A CN 117358245 B CN117358245 B CN 117358245B
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red mud
catalyst
shell
core structure
leaching
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CN117358245A (en
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钱彬彬
吴姝琴
李浩哲
陈思赟
许静茹
刘总堂
费正皓
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Yancheng Teachers University
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses a red mud-based thermal catalyst with a shell-core structure, a preparation method and application thereof, wherein red mud is used as a raw material, and metal cations in the red mud are leached by strong acid to obtain leaching mother liquor; then carrying out alkali precipitation on the leaching mother liquor to obtain hydroxide precipitation with metal ions; then carrying out hydrothermal treatment on the hydroxide precipitate to obtain nano alpha-Fe 2 O 3 A catalyst precursor; and finally, carrying out reduction reaction on the catalyst precursor in a reducing atmosphere to obtain the catalyst. The invention takes industrial solid waste-red mud as raw material, prepares Fe@Fe, M Fe with shell-core structure through controllable acid leaching, hydrothermal treatment and reduction activation 2 O 4 The catalyst has excellent high-temperature water gas shift hydrogen production effect, has stable structure in the catalytic process and is not easy to deactivate, and the ultra-high value utilization of large amount of industrial solid waste of red mud in the field of thermocatalytic hydrogen production is realized.

Description

Red mud-based thermal catalyst with shell-core structure, and preparation method and application thereof
Technical Field
The invention belongs to the field of solid waste treatment and thermocatalytic hydrogen production, and particularly relates to a red mud-based thermocatalyst with a shell-core structure, and a preparation method and application thereof.
Background
The red mud is Al 2 O 3 Industrial solid waste produced in the production process, 1 ton of Al is produced per production 2 O 3 Approximately 1.5-2 tons of red mud are produced. Since 2016, our country's Al 2 O 3 The production is always in the first place worldwide, wherein the production in 2022 is up to 7976 ten thousand tons, which is about 56.9% of the total world production, at least 1.19 hundred million tons of red mud are produced, and the accumulated stockpile amount is more than 6 hundred million tons, but the comprehensive utilization rate is only about 8%. Therefore, the high-value utilization of red mud is currently national and Al 2 O 3 The industry is in need of solving the problem. The red mud-based catalytic material is an important research direction for high-value utilization of the material. The red mud contains rich Fe and Al, a certain amount of Si, ti and Ca, a small amount of Na, K, mg, mn and Zr, and trace rare earth elements such as Sc, la and Ce, and the like, and particularly the red mud of high iron produced by the Bayer process, ferric oxide (alpha-Fe 2 O 3 ) The content is up to 30-60%. The application of various valuable metals or crystal minerals in the red mud to the catalytic industry can solve the pollution problem of the red mud and reduce the preparation cost of the catalyst.
The water gas shift reaction is industrial H production 2 Is a main means of (a). In the high temperature stage of actual production, the industrial catalyst is prepared by alpha-Fe 2 O 3 As a precursor, is converted into Fe after reduction and activation 3 O 4 Active center. Iron-chromium-based oxides (Cr) 2 O 3 -Fe 2 O 3 Precursor) Cr in the catalyst 3+ Can be converted into Cr which is easy to dissolve in water during the reaction 6+ It has strong biotoxicity. In the preparation and post-treatment of the catalyst, the catalyst is suitable for human healthThe ecological environment has great potential safety hazard. In recent years, research and development and preparation of Fe-based Cr-free catalysts are increasingly focused by researchers, and at present, al element can be used as a structural auxiliary agent to protect Fe 3 O 4 Is paid attention to by many researchers at home and abroad. In addition, the performance of the Fe-Al-based high-temperature water gas shift reaction catalyst can be further improved by doping a proper amount of active metal. The unit doping is such as Fe-Al-Ti, fe-Al-Ce, and the like, and the multiple doping is such as Fe-Al-Cu-M (M= Ca, mg, ce, la and Mn), and the like.
In view of this, red mud is a very promising raw material for the preparation of high temperature water gas reaction catalysts. The two main elements of Fe and Al in the red mud can be used as raw materials to synthesize Fe-Al-based catalyst to replace Fe-Cr catalyst. However, there is currently less research on red mud-based thermal catalysts.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides the high-temperature water gas reaction catalyst which takes red mud as a raw material, and utilizes the red mud which contains abundant impurity metals as active centers to improve the activity of the catalyst and realize the high added value utilization of the red mud in the thermocatalytic hydrogen production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the red mud-based thermal catalyst with the shell-core structure comprises the following steps:
(1) Taking red mud as a raw material, leaching metal cations in the red mud by using strong acid to obtain leaching mother liquor;
(2) Performing alkali precipitation on the leaching mother liquor obtained in the step (1) to obtain hydroxide precipitate with metal ions;
(3) Carrying out hydrothermal treatment on the hydroxide precipitate obtained in the step (2) to obtain nano alpha-Fe 2 O 3 A catalyst precursor;
(4) Carrying out reduction reaction on the catalyst precursor obtained in the step (3) in a reducing atmosphere to obtain red mud-based Fe@Fe (Fe, M) Fe 2 O 4 A thermal catalyst;
the red mud base Fe@Fe, M Fe 2 O 4 In the thermal catalyst, M is at least one element in Al, ti, mg, ca.
The two main elements of Fe and Al in the red mud can be used as raw materials to synthesize the Fe-Al-based catalyst to replace the Fe-Cr catalyst. In addition, red mud contains abundant impurity metals such as Ti, mn, zr, rare earth elements and the like, and can be used as an additional active center to form a Fe-Al-X (X=active metal) catalyst. Therefore, the applicant develops a high-efficiency and accurate strong acid leaching system, and researches the selective leaching rule of Fe, al, ti, ca, mg and other metals in the red mud acid leaching process. And taking the leaching solution as mother liquor to prepare alpha-Fe containing various active metals 2 O 3 A nanoparticle; using a reducing atmosphere to make the alpha-Fe 2 O 3 The nano precursor is reduced into Fe@Fe (M) Fe with a shell-core structure 2 O 4 (M is other active impurity metals except Fe in red mud, such as Al, mg, ca, ti and the like), and the special structure has physical protection effect on the catalyst to prevent the catalyst from being sintered and deactivated; in addition, various active valuable metals leached from the red mud form metal doping in the thermal reduction process, so that the activity of the catalyst is further improved.
Further, in the step (1), the red mud is industrial solid waste generated in the alumina industry; wherein SiO is 2 The content is 3-20wt%, al 2 O 3 The content is 10-25 wt%, fe 2 O 3 The content is 30-60 wt%, the CaO content is 2-8 wt%, and Na is 2 O content is 2-10wt% and TiO 2 The content is 0.1-10wt%.
Further, in the step (1), the strong acid is an inorganic acid (preferably 30%) with a volume concentration of 5-30%, and the inorganic acid comprises hydrochloric acid or sulfuric acid; the liquid-solid ratio of the inorganic acid to the red mud is 10:1-2 mL/g.
Further, in the step (1), the leaching reaction temperature is 25-85 ℃, the leaching reaction time is 15-120 min, preferably the leaching temperature is 60 ℃, and the leaching time is 80 min. An inorganic strong acid leaching method is used for extracting Fe, al, ti, mg, ca and other valuable active metal elements from the red mud.
In the step (2), naOH solution is adopted for the alkali precipitation, and the concentration of the NaOH solution is 3-5 mol/L. Regulating pH value (preferably pH value=6) with NaOH solution to obtain Fe (OH) containing Al, ti, mg, ca valuable metals 3 And (3) standing and aging the suspension in a water bath with a set temperature, placing the aged mixed solution in a high-pressure reaction kettle, and performing hydrothermal treatment at a set hydrothermal reaction temperature and time.
Further, in the step (3), the temperature of the hydrothermal treatment is 100-250 ℃ and the time is 8-48 hours; preferably, the hydrothermal treatment temperature is 150 ℃ and the time is 25 h. After the hydrothermal treatment is finished, taking out, cooling at room temperature, and finally centrifuging and drying to obtain the nano alpha-Fe 2 O 3 A catalyst precursor.
Further, in the step (4), the reducing atmosphere is a mixed atmosphere of hydrogen and nitrogen, wherein H 2 The volume concentration of (2) to (10), preferably 8%.
Further, the temperature of the reduction reaction is 300-500 ℃ and the time is 0.5-5 h; preferably 3.5. 3.5 h by reduction at 400 ℃.
Furthermore, the red mud-based Fe@Fe (M) Fe with shell-core structure prepared by the preparation method of the invention 2 O 4 Thermal catalysts are also within the scope of the present invention.
Furthermore, the invention also requires protection of the red mud-based Fe@Fe, M Fe with the shell-core structure 2 O 4 Preparation of H by hot catalyst in water gas shift reaction 2 Is used in the field of applications.
The beneficial effects are that: (1) The high-temperature strong acid leaching method adopted by the invention not only can extract Fe in the red mud, but also can controllably separate other active valuable metals in the red mud, such as Al, mg, ca and Ti, and the prepared Fe@Fe (M) Fe is subjected to hydrothermal treatment and reduction activation 2 O 4 (M is other active impurity metals except Fe in red mud, such as Al, mg, ca, ti and the like), and the catalyst has a special shell-core structure.
(2) The invention takes industrial solid waste-red mud as raw material, and passes through controllable acid leaching and hydrothermal treatmentPreparing Fe@Fe, M Fe with shell-core structure by reduction activation 2 O 4 The catalyst has excellent high-temperature water gas shift hydrogen production effect, has stable structure in the catalytic process, is not easy to inactivate, and realizes the ultrahigh value utilization of large amount of industrial solid wastes of red mud in the field of thermocatalytic hydrogen production.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 shows the α -Fe prepared after hydrothermal synthesis according to the present invention 2 O 3 XRD pattern of the catalyst precursor.
FIG. 2 is a diagram of Fe@Fe, M) Fe prepared after reductive activation 2 O 4 XRD pattern of the catalyst.
FIG. 3 is an XPS spectrum of the catalyst surface active impurities Al, ti, mg and Ca before and after reduction activation.
FIG. 4 is a schematic diagram of a red mud-based catalyst Fe@Fe, M Fe after reductive activation 2 O 4 Is a scanning transmission electron microscope picture and elemental line analysis.
FIG. 5 is a pure chemical reagent FeCl 3 •6H 2 alpha-Fe prepared from O 2 O 3 And (3) scanning transmission electron microscope pictures of the catalyst after the precursor is subjected to reduction and activation.
FIG. 6 is a comparison of the performance of two catalysts in a high temperature water gas shift reaction.
FIG. 7 is a comparison of specific surface areas of two catalyst precursors after reduction activation and after a high temperature water gas shift reaction.
Detailed Description
The invention will be better understood from the following examples.
The raw red mud raw material used in this example is derived from industrial solid waste generated in a certain alumina industry, and the element analysis results are shown in table 1.
4g of red mud sample is added into a beaker, 40 mL of concentrated hydrochloric acid with the concentration of 30vol% is poured into the beaker, the mixture is magnetically stirred at the speed of 400 r/min, water bath heating is carried out, and the water bath temperature is kept at 60 ℃.80 After min, the filter residue and the filtrate were collected by suction filtration, the filter residue was dried in a dry box, weighed 1.0717g, and the filtrate was collected in a solution bottle. Regulating pH to 6 with NaOH solution with concentration of 3 mol/L to obtain Fe (OH) 3 Placing the mixed solution in a high-pressure reaction kettle of 100 mL, taking out the mixed solution after setting the hydrothermal reaction temperature to 150 ℃ and the hydrothermal reaction time to 25 h, cooling the mixed solution at room temperature, centrifuging the obtained mixed solution by using a centrifuge, and drying the mixed solution at 80 ℃ by using a blast dryer for 10 h to obtain alpha-Fe 2 O 3 A catalyst precursor.
Taking 1 g alpha-Fe 2 O 3 The catalyst precursor is placed in a tube furnace, the reduction temperature is set to 400 ℃, the reduction time is 3.5H, and the H content is 8% 2 And 92% N 2 Is subjected to thermal reduction, and pure N is introduced after the reduction is finished 2 Until the temperature was reduced to room temperature.
First, various valuable metals in red mud leached by hydrochloric acid at high temperature are analyzed, and the results are shown in Table 1, alpha-Fe 2 O 3 The catalyst precursor contains a large amount of Fe, which shows that the leaching efficiency of Fe in the acid leaching process is high, and the element analysis of filter residues shows that the leaching rate of Fe in the process is as high as 98.03 percent. In addition, the precursor contains a certain amount of Al, mg, ca and Ti, which shows that hydrochloric acid has certain leaching effect on the active metals.
It can be seen that the inorganic acid leaching, hydrothermal synthesis and thermal reduction multiparameter regulation and control system provided by the invention: firstly, the leaching agent system can ensure the leaching efficiency of Fe in red mud and quantitatively leach other active valuable metals. When hydrochloric acid is used as a leaching agent, the leaching rate of Fe reaches 98.03% at the leaching temperature of 60 ℃; meanwhile, through the use of a hydrothermal synthesis multiparameter regulation system, on one hand, the alpha-Fe is ensured 2 O 3 On the other hand, controllable protectionPart of valuable active metal is reserved, and the prepared nano alpha-Fe 2 O 3 In the catalyst precursor, fe 2 O 3 93.52 percent of Al 2 O 3 3.24% of TiO 2 1.86%, caO 1.05%, mgO 0.09%, zrO 2 0.18% and 0.06% of other trace impurities.
TABLE 1 original Red mud, hydrothermally synthesized alpha-Fe 2 O 3 Elemental analysis of catalyst precursors and filter residues
FIG. 1 shows the alpha-Fe prepared by the present invention 2 O 3 X-ray diffraction analysis of a catalyst precursor, as can be seen from FIG. 1, the precursor is highly crystalline alpha-Fe 2 O 3 And the impurity metal does not generate additional diffraction peaks, which indicates that the impurity metal does not form a new crystalline phase, but is distributed in the form of solid solution in the alpha-Fe 2 O 3 In the lattice of the catalyst precursor.
And then carrying out analysis on the crystal structure, the surface state and the microscopic morphology of the catalyst after reduction and activation. FIG. 2 shows XRD analysis of the catalyst, which shows that the catalyst comprises Fe with high crystallinity 3 O 4 And metallic Fe; extensive analysis of the surface state of the catalyst by XPS, as shown in FIG. 3, the surface of the reduction-activated catalyst was enriched with a certain amount of Al, ti, mg and Ca, indicating that the reduction activity was accompanied by alpha-Fe 2 O 3 The catalyst precursor is reduced to Fe 3 O 4 Active center, originally solid-dissolved in alpha-Fe 2 O 3 Al, ti, mg and Ca in the crystal lattice of the precursor are gradually migrated by the secondary outer layer of the catalyst; furthermore, due to the outermost layer of Fe 3 O 4 Is further reduced to metallic Fe. The analysis structure of the scanning transmission electron microscope is shown in fig. 4, and it can be seen that the activated catalyst particles have a special structure of a shell core, and the structure of the element line scanning shows that part of impurity metals have higher content in the surface layer of the catalyst and are in an enrichment state. Thus, the catalyst finally forms Fe@Fe (M) Fe with a shell-core structure 2 O 4 (M is other active impurity metals except Fe in the red mud, such as Al, mg, ca, ti and the like). While using pure chemical reagents (e.g. FeCl 3 •6H 2 O) synthesized alpha-Fe 2 O 3 After the catalyst precursor is subjected to reduction activation, the microstructure does not show the special structure, and the analysis structure of the scanning transmission electron microscope is shown in fig. 5.
At a temperature of 350 ℃ and a space velocity of 40000 mL g -1 h -1 Under the same preparation conditions, the catalyst and the pure chemical agent FeCl for red mud synthesis are respectively prepared 3 •6H 2 The performance of the catalyst synthesized by O was tested, as shown in FIG. 6, and as a result, the conversion rate of CO of the surface red mud-based catalyst was as high as 96.37%, while the conversion rate of CO of the catalyst synthesized by the pure chemical was 63.85%. Therefore, the raw materials of the catalyst in the present invention: the industrial solid waste-red mud not only can replace chemical pure reagent (such as FeCl) 3 •6H 2 O), the hydrogen production performance of the prepared catalyst by high temperature water gas shift is superior to that of the catalyst synthesized by pure chemical reagents.
Finally, by analyzing the specific surface area of the catalyst before and after the reaction, the results are shown in FIG. 7, indicating Fe@Fe (M) Fe having a shell-core structure 2 O 4 (M is other active impurity metals except Fe in red mud, such as Al, mg, ca, ti and the like), and the Fe of the outer shell layer can be not only matched with the MFe 2 O 4 Forms a rapid electron channel between them to accelerate the reaction, and can protect the structure of the catalyst and prevent the catalyst from sintering (the specific surface areas before and after the reaction are 55.36 and 49.81 m respectively 2 /g); by pure chemical agent FeCl 3 •6H 2 The O synthesis catalyst has no outer protection, not only reduces electron transfer in the reaction process, but also reduces specific surface area (the specific surface areas before and after the reaction are 30.62 and 9.74 m respectively) 2 /g), and finally deactivated.
The experiments show that the alpha-Fe is reduced 2 O 3 The nano catalyst precursor successfully prepares Fe@Fe (M) Fe with shell-core structure 2 O 4 (M is other active impurity metals except Fe in red mud, such as Al, mg, ca, ti, etc.), at a temperature of 350 ℃ and a space velocity of 40000 mL g -1 h -1 Under the catalysis condition, the conversion rate of CO is up to 96.37%; and the raw materials of the invention are as followsIndustrial solid waste-red mud, no chemical pure reagent containing Fe is needed.
The invention provides a thinking and a method for preparing a red mud-based thermal catalyst with a shell-core structure, and particularly provides a method and a plurality of ways for realizing the technical scheme, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by one of ordinary skill in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.

Claims (8)

1. The preparation method of the red mud-based thermal catalyst with the shell-core structure is characterized by comprising the following steps of:
(1) Taking red mud as a raw material, leaching metal cations in the red mud by using strong acid to obtain leaching mother liquor;
(2) Performing alkali precipitation on the leaching mother liquor obtained in the step (1) to obtain hydroxide precipitate with metal ions;
(3) Carrying out hydrothermal treatment on the hydroxide precipitate obtained in the step (2) to obtain nano alpha-Fe 2 O 3 A catalyst precursor;
(4) Carrying out reduction reaction on the catalyst precursor obtained in the step (3) in a reducing atmosphere to obtain red mud-based Fe@Fe (Fe, M) Fe 2 O 4 A thermal catalyst;
the red mud base Fe@Fe, M Fe 2 O 4 In the thermal catalyst, M is at least one element in Al, ti, mg, ca;
in the step (1), the strong acid is inorganic acid with the volume concentration of 5-30%, and comprises hydrochloric acid or sulfuric acid; the liquid-solid ratio of the inorganic acid to the red mud is 10:1-5 mL/g;
in the step (4), the reducing atmosphere is a mixed atmosphere of hydrogen and nitrogen, wherein H 2 The volume concentration of (2-10%).
2. The red mud-based heat with a shell-core structure according to claim 1The preparation method of the catalyst is characterized in that in the step (1), the red mud is industrial solid waste generated in the alumina industry; wherein SiO is 2 The content is 3-20wt%, al 2 O 3 The content is 10-25 wt%, fe 2 O 3 The content is 30-60 wt%, the CaO content is 2-8 wt%, and Na is 2 O content is 2-10wt% and TiO 2 The content is 0.1-10wt%.
3. The method for preparing the red mud-based thermal catalyst with the shell-core structure according to claim 1, wherein in the step (1), the leaching reaction temperature is 25-85 ℃, and the leaching reaction time is 15-120 min.
4. The method for preparing the red mud-based thermal catalyst with the shell-core structure according to claim 1, wherein in the step (2), naOH solution is adopted for alkali precipitation, and the concentration of the NaOH solution is 3-5 mol/L.
5. The method for preparing the red mud-based thermal catalyst with the shell-core structure according to claim 1, wherein in the step (3), the temperature of the hydrothermal treatment is 100-250 ℃ and the time is 8-48 hours.
6. The method for preparing the red mud-based thermal catalyst with the shell-core structure according to claim 1, wherein in the step (4), the temperature of the reduction reaction is 300-500 ℃ and the time is 0.5-5 h.
7. The red mud-based Fe@Fe (M) Fe with shell-core structure prepared by any one of the preparation methods of claims 1-6 2 O 4 A thermal catalyst.
8. The red mud-based Fe@Fe, M) Fe with shell-core structure of claim 7 2 O 4 Preparation of H by hot catalyst in water gas shift reaction 2 Is used in the field of applications.
CN202311671235.9A 2023-12-07 2023-12-07 Red mud-based thermal catalyst with shell-core structure, and preparation method and application thereof Active CN117358245B (en)

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