CN111346641A - Doped α -ferric oxide, preparation method thereof and application thereof in hydrogenation reaction - Google Patents

Doped α -ferric oxide, preparation method thereof and application thereof in hydrogenation reaction Download PDF

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CN111346641A
CN111346641A CN202010288540.XA CN202010288540A CN111346641A CN 111346641 A CN111346641 A CN 111346641A CN 202010288540 A CN202010288540 A CN 202010288540A CN 111346641 A CN111346641 A CN 111346641A
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邹吉军
高睿杰
潘伦
张香文
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Tianjin University
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Abstract

The invention provides α -doped ferric oxide, a preparation method thereof and application thereof in hydrogenation reaction, and relates to the technical field of hydrogenation, wherein α -Fe is doped2O3Comprising α -Fe doped with 3d transition metal2O3α -Fe doped with 3d transition metal2O3Can realize excellent catalytic hydrogenation effect, can be applied to a fixed bed, resists high temperature and high pressure, realizes the hydrogenation of a plurality of substrates (nitrobenzene compounds, polycyclic aromatic hydrocarbons, olefins, alkynes, aldehyde carbonyls and the like) containing different functional groups, and is α -Fe doped with 3d transition metal2O3The price is low, and the pollution is not easy to generate.

Description

Doped α -ferric oxide, preparation method thereof and application thereof in hydrogenation reaction
Technical Field
The invention relates to the technical field of hydrogenation, in particular to doped α -ferric oxide, a preparation method thereof and application thereof in hydrogenation reaction.
Background
The heterogeneous catalytic hydrogenation reaction is an important step in industrial production, and according to statistics, at least one step of hydrogenation reaction is involved in 25% of chemical production, so that the efficiency of the hydrogenation reaction directly determines the economic benefit of the whole production process, and how to design a high-efficiency and low-cost hydrogenation catalyst is the key point of research in the field. Research shows that in the hydrogenation reaction, the dissociation and desorption of hydrogen are key factors determining the hydrogenation reaction rate. The common hydrogenation catalyst mainly takes noble metals such as palladium, platinum and the like in a reduction state and alloys as main active components, and the expensive price and the rare reserves of the noble metals also limit the scale use of the catalyst. More importantly, in some fine chemical and pharmaceutical industries, the use of noble metal catalysts can cause noble metal pollution, which is not favorable for the separation and purification of chemicals.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide α -Fe doping2O3Use of (α -iron trioxide) in hydrogenation with 3d transition metal doped α -Fe2O3Can realize excellent catalytic hydrogenation effect, can be applied to a fixed bed, resists high temperature and high pressure, can realize the hydrogenation of a plurality of substrates (nitrobenzene compounds, polycyclic aromatic hydrocarbons, olefins, alkynes, aldehyde carbonyls and the like) containing different functional groups, and can realize the 3d transition metal doped α -Fe2O3The price is low, and the pollution is not easy to generate.
The invention provides α -Fe doping2O3Application in hydrogenation, the doping α -Fe2O3Comprising α -Fe doped with 3d transition metal2O3。
Further, the 3d transition metal includes at least one of Mn, Cr, Co, Ni, Cu, and Zn.
Further, the 3d transition metal is Zn.
Further, α -Fe was doped2O3The molar ratio of the 3d transition metal to the iron element in (1) is (0-0.5): 1.
further, the hydrogenation comprises hydrogenating a substrate comprising at least one of a carbonyl group, a carbon-carbon double bond, a carbon-carbon triple bond, a nitro group, and an aromatic hydrocarbon.
Further, the substrate includes at least one of nitrobenzene, benzaldehyde, styrene, phenylacetylene, and toluene.
Further, the pressure of the hydrogenation is 8-12 bar;
preferably, the hydrogenation temperature is 90-450 ℃.
Doped α -Fe2O3Comprising α -Fe doped with 3d transition metal2O3Doped α -Fe2O3The molar ratio of the 3d transition metal to the iron element in (1) is (0-0.5): 1.
further, the 3d transition metal includes at least one of Co, Ni, Cu, and Zn, preferably Zn.
α -Fe doped as described above2O3The preparation method comprises the following steps:
doping of 3d transition metals to α -Fe2O3Performing the following steps;
preferably, the 3d transition metal is doped to α -Fe2O3Comprises the following steps:
mixing an iron source, 3d transition metal salt and water, and carrying out hydrothermal reaction;
calcining the product of the hydrothermal reaction to dope the 3d transition metal to α -Fe2O3Performing the following steps;
preferably, the temperature of the hydrothermal reaction is 80-120 ℃, and the time is 12-24 h;
preferably, the temperature of the calcination is 350-460 ℃.
Compared with the prior art, the invention can at least obtain the following beneficial effects:
α-Fe2O3is a nontoxic, harmless, cheap and easily available substance, is an ideal catalytic material, but has a high active hydrogen energy barrier, and α -Fe is not applied to hydrogenation reaction in the prior art2O3However, in the present invention, the inventors have unexpectedly found that α -Fe can be doped with a 3d transition metal element having a high d orbital electron number2O3Doped α -Fe to improve its hydrogen activation capability2O3The hydrogenation activity is improved by times, a plurality of substrates (nitrobenzene compounds, polycyclic aromatic hydrocarbon, olefin, alkyne, aldehyde carbonyl and the like) containing different functional groups can be hydrogenated, the catalyst is resistant to high temperature and high pressure, and can be used for a fixed bed, wherein the 3d transition metal element in the catalyst is doped with α -Fe2O3The applicable hydrogenation system is wide, and can be used for hydrogenation of C-O, C ═ C and O-N ═ O, saturation of aromatic hydrocarbons, and is less likely to cause contamination.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is the Zn-doped α -Fe of example 12O3XRD spectrum of (1);
FIG. 2 Zn doped α -Fe in example 12O3And (4) a tolerance test result chart for recycling.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In one aspect of the invention, the invention provides a doped α -Fe2O3Application in hydrogenation, the doping α -Fe2O3Comprising α -Fe doped with 3d transition metal2O3。
α-Fe2O3Is a nontoxic, harmless, cheap and easily available substance, is an ideal catalytic material, but has a high active hydrogen energy barrier, and α -Fe is not applied to hydrogenation reaction in the prior art2O3However, in the present invention, the inventors have unexpectedly found that α -Fe can be doped with a 3d transition metal element having a high d orbital electron number2O3Doped α -Fe to improve its hydrogen activation capability2O3The hydrogenation activity is improved by times, and the 3d transition metal element in the invention is doped with α -Fe2O3The applicable hydrogenation system is wide, and can be used for hydrogenation of C-O, C ═ C and O-N ═ O, saturation of aromatic hydrocarbons, and is less likely to cause contamination.
In some embodiments of the invention, the 3d transition metal comprises at least one of Mn, Cr, Co, Ni, Cu and Zn. Therefore, the material has wide sources and low price, and belongs to cleaner materials.
In some preferred embodiments of the invention, the 3d transition metal is Zn, thus, Zn doped α -Fe2O3The hydrogenation performance of (2) is better.
In some embodiments of the invention, α -Fe is doped2O3The molar ratio of the 3d transition metal to the iron element in (0-0.5): 1, for example α -Fe2O3The molar ratio of the iron element in (b) to the 3d transition metal may be (0.125, 0.25, 0.375, 0.5): 1, etc.
In some embodiments of the invention, the hydrogenation comprises hydrogenation of a substrate comprising at least one of a carbonyl group (C ═ O), a carbon-carbon double bond (C ═ C), a carbon-carbon triple bond, a nitro group (O-N ═ O), and an aromatic hydrocarbon. Therefore, the hydrogenation system is wide and suitable for large-scale application.
In some embodiments of the invention, the substrate comprises at least one of nitrobenzene, benzaldehyde, styrene, phenylacetylene, and toluene. Therefore, the hydrogenation system is wide and suitable for large-scale application.
In some embodiments of the invention, the hydrogenation is at a pressure of 8-12bar (e.g., 8bar, 9bar, 10bar, 11bar, 12bar, etc.). For the pressure of above-mentioned hydrogenation, when the pressure of hydrogenation is too low, then the hydrogenation effect is not good, and when the pressure of hydrogenation was too high, the hydrogenation effect promoted not obviously, the extravagant energy.
In some embodiments of the invention, the hydrogenation temperature is 90-450 ℃ (e.g., can be 90 ℃, 100 ℃, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, or 450 ℃, etc.). When the hydrogenation temperature is lower than 90 ℃, the hydrogenation effect is poor relative to the hydrogenation temperature; when the hydrogenation temperature is higher than 450 ℃, the hydrogenation reaction is not obviously improved.
In another aspect of the invention, the invention provides a doped α -Fe2O3Doped α -Fe2O3Comprising α -Fe doped with 3d transition metal2O3Doped α -Fe2O3The molar ratio of the 3d transition metal to the iron element in (2) is (0-0).5)：1。
Note that the above 3d transition metal doped α -Fe2O3Consistent with the foregoing description, further description is not provided herein.
In some embodiments of the invention, the 3d transition metal comprises at least one of Mn, Cr, Co, Ni, Cu and Zn, preferably Zn, whereby α -Fe is doped2O3The hydrogenation performance of (2) is excellent.
In another aspect of the invention, the invention provides a doped α -Fe alloy as described above2O3The preparation method comprises doping 3d transition metal to α -Fe2O3In (1). Therefore, the operation is simple and convenient, and the realization is easy.
In some embodiments of the invention, the 3d transition metal is doped to α -Fe2O3Comprises mixing iron source, 3d transition metal salt and water, performing hydrothermal reaction, and calcining the product obtained by the hydrothermal reaction to dope the 3d transition metal into α -Fe2O3In (1). Therefore, the operation is simple and convenient, and the realization is easy.
In some embodiments of the present invention, the hydrothermal reaction is performed at a temperature of 80-120 ℃ (for example, 80 ℃, 100 ℃, or 120 ℃ and the like) for 12-24h (for example, 12h, 14h, 16h, 18h, 20h, 22h, or 24h and the like). When the temperature of the hydrothermal reaction is too low or the time is too short, the formation of iron hydroxide is not facilitated; when the temperature of the hydrothermal reaction is too high or the time is too long, the preparation effect of the catalyst is not obviously improved.
In some embodiments of the present invention, the temperature of calcination is 350-.
In some embodiments of the invention, α -Fe is doped2O3The preparation method comprises the following steps:
weighing ferric trichloride and metal-doped chloride in a certain proportion, adding a certain amount of deionized water, heating in an environment of 80-120 ℃ for hydrolysis reaction for 12-24h, and reactingThe obtained hydroxide is put into 450 ℃ for roasting to obtain doped α -Fe2O3A hydrogenation catalyst.
Some embodiments of the present invention will be described in detail below with reference to specific examples. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
Examples
Example 1
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 3mmol ferric chloride and 1mmol zinc chloride, placing in a polytetrafluoroethylene lining, adding 60mL deionized water, stirring uniformly, placing in an environment of 95 ℃ for heating for hydrolysis reaction, reacting for 12 hours, cooling to room temperature to obtain hydroxide, and roasting the obtained hydroxide at 450 ℃ for 2 hours to obtain Zn-doped α -Fe2O3。
The resulting Zn-doped α -Fe2O3The XRD spectrum of the crystal is shown in figure 1, and figure 1 shows α -Fe2O3Characteristic peak and no ZnO peak appear, which proves that Zn is successfully doped into α -Fe2O3A crystal lattice. ICP (inductively coupled plasma test) results demonstrate Fe: zn (molar ratio) was 3.1: 1.1.
The obtained Zn-doped α -Fe2O3The method is used for hydrogenation reaction of nitrobenzene, benzaldehyde, styrene, phenylacetylene and toluene, and comprises the following steps:
10mg of Zn-doped α -Fe of this example was charged in an autoclave2O30.5mmol of reaction substrate and 5ml of absolute ethyl alcohol, then sealing the reaction kettle, introducing high-purity nitrogen to 20bar, and repeating the operation three times, then introducing high-purity hydrogen to 20bar, and repeating the operation three times, wherein the reaction temperature is 100 ℃. The time required for the conversion of the reaction substrate to 100% was measured, and the results of the hydrogenation reaction are shown in Table 1 below. In a fixed bed reactor, 200mg of catalyst was diluted with 2g of quartz sand. The solution of cyclohexane containing 1g of the reactants was bubbled into the reactor at a reaction pressure of 60bar and a space velocity of 84000mL g-1h-1Left and right. The results of the hydrogenation reaction are shown in Table 2 below. In addition, the catalyst can be usedThe specific components of the coal liquefaction oil after hydrodesulfurization and aromatics saturation are shown in Table 3. The coal liquefaction oil containing 30-40% of aromatic hydrocarbon and 439ppm of sulfur impurity is subjected to hydrogenation treatment (reaction conditions are 50bar hydrogen and 360 ℃), the aromatic hydrocarbon can be completely saturated, and the sulfur removal efficiency reaches 100%.
TABLE 1
Substrate Product of Reaction time (hours) Conversion (%)
Nitrobenzene Aniline 4 100
Benzaldehyde Benzyl alcohol 5 100
Styrene (meth) acrylic acid ester Ethylbenzene production 1 100
Phenylacetylene Ethylbenzene production 2 100
TABLE 2
Figure BDA0002449494810000071
Figure BDA0002449494810000081
TABLE 3
Figure BDA0002449494810000082
The Zn-doped α -Fe obtained in this example2O3For evaluation of the durability of the catalyst to recycling, 10mg of Zn-doped α -Fe2O30.5mmol nitrobenzene, 5ml absolute ethanol, hydrogen partial pressure of 10bar, tolerance test results are shown in figure 2, it can be seen that after 8 cycles of use, the reactant conversion rate remains substantially unchanged, the selectivity is greater than 97%, and the Zn-doped α -Fe can be seen2O3Maintains higher activity and has better industrial application prospect.
Example 2
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 3.5mmol ferric chloride and 0.5mmol zinc chloride, placing in a polytetrafluoroethylene lining, adding 60mL deionized water, stirring well, placing in an environment of 95 ℃ for heating for hydrolysis reaction, cooling to room temperature after reaction for 12 hours to obtain hydroxide, and roasting the obtained hydroxide at 450 ℃ for 2 hours to obtain Zn-doped α -Fe2O3(ii) a ICP characterization demonstrated that Fe: zn (molar ratio) was 7.1: 1.
Example 3
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 2.5mmol ferric chloride and 1.5mmol zinc chloride, placing in polytetrafluoroethylene lining, adding 60mL deionized water, stirring, and heating at 95 deg.C for hydrolysis reactionReacting for 12 hours, cooling to room temperature to obtain hydroxide, and roasting the obtained hydroxide at 450 ℃ for 2 hours to obtain Zn-doped α -Fe2O3(ii) a ICP characterization demonstrated that Fe: zn (molar ratio) was 5.3: 3.2.
Example 4
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 2.0mmol of ferric chloride and 2.0mmol of zinc chloride, placing the ferric chloride and the 2.0mmol of zinc chloride in a polytetrafluoroethylene lining, adding 60mL of deionized water, stirring uniformly, placing the polytetrafluoroethylene lining in an environment with the temperature of 95 ℃ for heating for hydrolysis reaction, cooling to room temperature after reacting for 12 hours to obtain hydroxide, and roasting the obtained hydroxide at the temperature of 450 ℃ for 2 hours to obtain Zn-doped α -Fe2O3(ii) a ICP characterization demonstrated that Fe: zn (molar ratio) was 1.1: 0.95.
Example 5
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 3.0mmol of ferric chloride and 1.0mmol of cupric chloride, placing into a polytetrafluoroethylene lining, adding 60mL of deionized water, stirring uniformly, placing into an environment of 95 ℃, heating for hydrolysis reaction, reacting for 12 hours, cooling to room temperature to obtain hydroxide, and roasting the obtained hydroxide at 450 ℃ for 2 hours to obtain Cu-doped α -Fe2O3(ii) a ICP characterization demonstrated that Fe: cu (molar ratio) was 3.05: 0.98.
Example 6
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 3.0mmol of ferric chloride and 1.0mmol of nickel chloride, placing the ferric chloride and the nickel chloride into a polytetrafluoroethylene lining, adding 60mL of deionized water, stirring uniformly, placing the polytetrafluoroethylene lining into an environment with the temperature of 95 ℃, heating for hydrolysis reaction, reacting for 12 hours, cooling to room temperature to obtain hydroxide, and roasting the obtained hydroxide at the temperature of 450 ℃ for 2 hours to obtain Ni-doped α -Fe2O3(ii) a ICP characterization demonstrated that Fe: ni (molar ratio) was 3.12: 0.95.
Example 7
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 3.0mmol of ferric chloride and 1.0mmol of cobalt chloride, placing the ferric chloride and the 1.0mmol of cobalt chloride in a polytetrafluoroethylene lining, adding 60mL of deionized water, stirring uniformly, placing the polytetrafluoroethylene lining in an environment with the temperature of 95 ℃ for heating and hydrolysis reaction, cooling to room temperature after reaction for 12 hours to obtain hydroxide, and roasting the obtained hydroxide at the temperature of 450 ℃ for 2 hours to obtain Co-doped α -Fe2O3(ii) a ICP characterization demonstrated that Fe: co (molar ratio) was 3.09: 1.01.
Example 8
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 3.0mmol of ferric chloride and 1.0mmol of manganese chloride, placing the ferric chloride and the 1.0mmol of manganese chloride in a polytetrafluoroethylene lining, adding 60mL of deionized water, stirring uniformly, placing the polytetrafluoroethylene lining in an environment with the temperature of 95 ℃ for heating for hydrolysis reaction, cooling to room temperature after reacting for 12 hours to obtain hydroxide, and roasting the obtained hydroxide at the temperature of 450 ℃ for 2 hours to obtain Mn-doped α -Fe2O3(ii) a ICP characterization demonstrated that Fe: mn (molar ratio) was 3.09: 1.00.
Example 9
Doped α -Fe2O3The preparation method comprises the following steps:
weighing 3.0mmol of ferric chloride and 1.0mmol of chromium chloride, placing the ferric chloride and the chromium chloride into a polytetrafluoroethylene lining, adding 60mL of deionized water, stirring uniformly, placing the polytetrafluoroethylene lining into an environment with the temperature of 95 ℃, heating for hydrolysis reaction, reacting for 12 hours, cooling to room temperature to obtain hydroxide, and roasting the obtained hydroxide at the temperature of 450 ℃ for 2 hours to obtain Cr-doped α -Fe2O3(ii) a ICP characterization demonstrated that Fe: cr (molar ratio) was 3.02: 1.03.
Example 10
Doped α -Fe2O3The preparation method of (1) is the same as that of example 1, except that the ratio of Fe: zn (molar ratio) is 8: 0.5.
example 11
Doped α -Fe2O3The preparation method of (1) is the same as that of example 1, except that the ratio of Fe: zn (molar ratio) is 10: 0.1.
example 12
Doped α -Fe2O3System of (1)The preparation method is the same as example 1, except that Fe: zn (molar ratio) 0.5: 6.
comparative example 1
α-Fe2O3The preparation method comprises the following steps:
weighing 4.0mmol of ferric chloride, placing the ferric chloride in a polytetrafluoroethylene lining, adding 60mL of deionized water, stirring uniformly, placing the polytetrafluoroethylene lining in an environment with the temperature of 95 ℃ for heating for hydrolysis reaction, cooling to room temperature after reacting for 12 hours to obtain hydroxide, and roasting the obtained hydroxide at the temperature of 450 ℃ for 2 hours to obtain α -Fe2O3。
α -Fe doping Using examples 1-122O3And α -Fe in comparative example 12O3The styrene is hydrogenated (the hydrogenation product is phenylethane), and the specific operation step of the hydrogenation condition is that 10mg of doped α -Fe in the examples 1 to 10 are respectively added into a high-pressure reaction kettle2O3And α -Fe in comparative example 12O30.5mmol of reaction substrate (styrene) and 5ml of absolute ethyl alcohol, then sealing the reaction kettle, introducing high-purity nitrogen to 20bar, performing the operation for three times, introducing high-purity hydrogen to 20bar, and repeating the operation for three times, wherein the reaction temperature is 100 ℃, the time is 0.5h, the system pressure is 10bar, and the hydrogenation result is shown in the following table 4:
TABLE 4
Figure BDA0002449494810000111
Figure BDA0002449494810000121
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. Doped α -Fe2O3Use in hydrogenation, characterized in that said doping α -Fe2O3Comprising α -Fe doped with 3d transition metal2O3。
2. Use according to claim 1, wherein the 3d transition metal comprises at least one of Mn, Cr, Co, Ni, Cu and Zn.
3. Use according to claim 2, wherein the 3d transition metal is Zn.
4. Use according to any one of claims 1 to 3, characterized in that α -Fe is doped2O3The molar ratio of the 3d transition metal to the iron element in (1) is (0-0.5): 1.
5. the use of claim 4, wherein the hydrogenation comprises hydrogenation of a substrate comprising at least one of a carbonyl group, a carbon-carbon double bond, a carbon-carbon triple bond, a nitro group, and an aromatic hydrocarbon.
6. The use of claim 5, wherein the substrate comprises at least one of nitrobenzene, benzaldehyde, styrene, phenylacetylene, and toluene.
7. Use according to claim 1, 2, 3, 5 or 6, characterized in that the hydrogenation is carried out at a pressure of 8-12 bar;
preferably, the hydrogenation temperature is 90-450 ℃.
8. Doped α -Fe2O3Characterized by comprising α -Fe doped with 3d transition metal2O3Doped α -Fe2O3The molar ratio of the 3d transition metal to the iron element in (a) is (0-0.5)：1。
9. Doped α -Fe according to claim 82O3Wherein the 3d transition metal includes at least one of Mn, Cr, Co, Ni, Cu and Zn, preferably Zn.
10.α -Fe doped according to claim 8 or 92O3The method for preparing (1) is characterized by comprising the following steps:
doping of 3d transition metals to α -Fe2O3Performing the following steps;
preferably, the 3d transition metal is doped to α -Fe2O3Comprises the following steps:
mixing an iron source, 3d transition metal salt and water, and carrying out hydrothermal reaction;
calcining the product of the hydrothermal reaction to dope the 3d transition metal to α -Fe2O3Performing the following steps;
preferably, the temperature of the hydrothermal reaction is 80-120 ℃, and the time is 12-24 h;
preferably, the temperature of the calcination is 350-460 ℃.
CN202010288540.XA 2020-04-14 2020-04-14 Doped α -ferric oxide, preparation method thereof and application thereof in hydrogenation reaction Pending CN111346641A (en)

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