Isolated Ni atom-acid site bifunctional catalyst and preparation method and application thereof

Abstract

The invention discloses a bifunctional catalyst for isolating Ni atoms and acid sites as well as a preparation method and application of the bifunctional catalyst, and belongs to the field of fine chemical engineering. Through a reducing atmosphere heat treatment technology, Al2O3-ASW with the surface rich in unsaturated coordination Al < 3 + > and weak acid sites is obtained as a carrier, active metal Ni atoms and second metal M are stably loaded on the surface of the carrier, and after reduction treatment, the NiM / Al2O3-ASW bifunctional catalyst with discontinuous geometric isolation of the active metal Ni atoms and an optimized electronic structure is obtained. The Niiso-ASW double-site catalytic dechlorination catalyst has the advantages that the catalytic dechlorination effect is good, agglomeration of active metal is inhibited, meanwhile, the accessibility of double active sites is also improved, the Niiso-ASW double-site shows a strong synergistic effect, and the dechlorination catalytic activity and selectivity are jointly improved.

Description

Technical Field

[0001] The present invention belongs to the field of fine chemicals, and in particular relates to a cluster-core isolated and dispersed shaped catalyst, a preparation method and an application thereof. The catalyst is mainly used in the selective dechlorination reaction process of 1,1,1,3-tetrachloropropane. Background Art

[0002] With the rapid development of human society, the amount of chlorofluorocarbons (CFCs) in the ozone layer has increased due to human activities (such as the use of refrigerants and sprays), leading to severe ozone depletion and increasingly serious environmental problems. Emissions of refrigerants such as Freon have a significant impact on ozone layer depletion and the greenhouse effect. Therefore, the development of novel refrigerants with low global warming potential (GWP) is becoming increasingly important. 1,1,3-Trichloropropene, as a key intermediate in the synthesis of a new environmentally friendly refrigerant (HFO-1234yf), has attracted widespread attention. It is primarily prepared by catalytic selective dechlorination of 1,1,1,3-tetrachloropropane.

[0003] Supported catalysts have become a research hotspot in industry and academia due to their advantages such as small amount of catalytically active components, low preparation cost, and high reaction selectivity. However, it is difficult to optimize the adsorption state of multiple intermediates at a single active site, resulting in limited catalytic activity and selectivity. Bifunctional catalysts have two active sites, and synergistic catalysis can effectively improve the activity and selectivity of catalytic reactions. In this type of catalyst system, the influence of the support material on the catalytic performance is crucial. Its physicochemical properties (such as specific surface area, pore structure, surface acidity and alkalinity, etc.) can significantly regulate the dispersion state of the active components, the electronic structure, and the adsorption-desorption behavior of the reactant molecules, thereby determining the efficiency and selectivity of the catalytic reaction. However, the controllable construction of synergistic sites of bifunctional catalysts remains challenging.

[0004] Based on this, the present invention obtains a surface rich in unsaturated coordinated Al by reducing atmosphere heat treatment technology. 3+ and Al2O3-AS with weak acid sites W As a carrier, the active metal Ni atoms and the second metal M are stably loaded on the carrier surface. After reduction treatment, NiM / Al2O3-AS with geometrically isolated and discontinuous active metal Ni atoms and optimized electronic structure is obtained. W Bifunctional catalysts inhibit the agglomeration of active metals and also improve the accessibility of dual active sites. iso -AS W The dual sites exhibit strong synergistic effects, achieving a joint improvement in dechlorination catalytic activity and selectivity. Summary of the Invention

[0005] The present invention aims to provide an isolated Ni atom-acid site bifunctional catalyst and a preparation method and application thereof.

[0006] 2. The selective dechlorination catalyst provided by the present invention is represented by NiM / Al2O3-AS W , wherein M represents a second metal selected from Fe, Co, Zn, and Cu; the active metal Ni accounts for 0.03 to 5.00 wt.% of the catalyst mass; Al2O3-AS W It has a surface unsaturated coordination structure and is rich in weak acid sites (AS W ) of different crystal forms (α-Al2O3, γ-Al2O3, θ-Al2O3, δ-Al2O3) of alumina support; the structural characteristics of the catalyst are: the active metal Ni and M are alloyed to achieve the isolation of Ni sites and stably load on the alumina surface, Ni iso With the adjacent weakly acidic sites on the alumina surface (AS W ) synergistically form bifunctional Ni iso -AS W Active site.

[0007] The isolated Ni atom-acid site bifunctional catalyst and its preparation method provided by the present invention are characterized by being prepared according to the following specific steps:

[0008] A. Place Al2O3 in a tube furnace and introduce a reducing atmosphere for activation treatment to obtain unsaturated and weakly acidic AS. W Alumina support with sites (Al2O3-AS W ).

[0009] The reducing atmosphere is introduced in a continuous manner or in an intermittent pulse manner.

[0010] The crystal phase of Al2O3 is one of α-Al2O3, γ-Al2O3, θ-Al2O3, and δ-Al2O3;

[0011] The reducing atmosphere is one of H2 / N2, H2, CO / N2; the treatment temperature is 300-1200℃, the holding time is 2-5h, and the heating rate is 2-25℃min -1 ;

[0012] B. A mixed salt solution prepared by dissolving a soluble nickel salt and a soluble M salt in a molar ratio of 1.5 to 1 / 5 in 20 mL of deionized water, and the unsaturated and weakly acidic Al2O3-AS obtained in step A is added according to the theoretical loading of active metal Ni in the catalyst mass of 0.03 to 5.00 wt.%. WThe carrier is added to the above mixed salt solution; the obtained uniform slurry is impregnated by ultrasound-assisted temperature control strategy, stirred at 30-80 ° C at 200-500 rpm for 4-6 hours until it becomes viscous, and dried in a constant temperature drying oven at 50-120 ° C for 8-24 hours to obtain Ni 2+ M x+ / Al2O3-AS W Precursor.

[0013] The soluble nickel salt is one of Ni(NO3)2·6H2O, NiCl2·6H2O, NiSO4·6H2O, and Ni(CH3COO)2·4H2O;

[0014] The soluble M salt is one of Fe(NO3)3·9H2O, Fe2(SO4)3·5H2O, FeCl3·6H2O, Fe(OH)(CH3COO)2, CuSO4·5H2O, CuCl2·2H2O, Cu(NO3)2·3H2O, (CH3COO)2Cu·H2O, ZnSO4·7H2O, Zn(NO3)2·6H2O, (CH3COO)2Zn·2H2O, Co(NO3)2·6H2O, CoCl2·6H2O, and CoSO4·7H2O;

[0015] C. Ni obtained in step A 2+ M x+ / Al2O3-AS W The precursor is placed in a tube furnace and heated to 400-800°C at a rate of 2-25°C / min in a reducing atmosphere for 1-5h with a gas flow rate of 40-70mL / min. After cooling to room temperature, Ni iso -AS W NiM / Al2O3-AS with dual-functional active sites W catalyst.

[0016] The reducing atmosphere is one of H2 / N2, H2, and CO / N2;

[0017] The preparation method is characterized by: using unsaturated and weakly acidic Al2O3-AS W As a carrier, the unsaturated coordination of Al on the surface of alumina is achieved by regulating the heat treatment conditions of alumina in a reducing atmosphere. 3+ The number of weak acid sites is controllable, and the number of weak acid sites is 300-500 mmol / g. By further regulating the impregnation stability and atmosphere treatment conditions, the active metal Ni is isolated and stably loaded on the carrier surface, thereby constructing Ni with the weak acid sites on the alumina surface. iso -AS W Double synergistic sites and simple preparation process. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 Al2O3-AS prepared in Example 1 W of 27 Al NMR spectrum shows that under the action of heat treatment in reducing atmosphere, Al2O3 presents rich penta-coordinated Al 3+ .

[0019] Figure 2 Al2O3-AS prepared in Example 1 W From the NH3-TPD spectrum, it can be seen that the surface acid structure is significantly affected by the heat treatment in a reducing atmosphere, showing more abundant weak acid sites.

[0020] Figure 3 Ni3Fe2 / Al2O3-AS prepared in Example 1 W HRTEM and EDS line scan images of the bifunctional catalyst show that the metal nanoparticles are evenly distributed in the Al2O3-AS W There is no obvious agglomeration phenomenon and an alloy structure is formed.

[0021] Figure 4 Ni3Fe2 / Al2O3-AS prepared in Example 1 W CO-IR spectrum of bifunctional catalyst. It can be seen that Ni3Fe2 / Al2O3-AS W The active metal Ni in the bifunctional catalyst is isolated.

[0022] Figure 5 Ni3Fe2 / Al2O3-AS prepared in Example 1 W The bifunctional catalyst has a good catalytic performance in the selective dechlorination of 1,1,1,3-tetrachloropropane. Under the condition of complete conversion of 1,1,1,3-tetrachloropropane, the selectivity of the catalyst for 1,1,3-trichloropropene can reach 94%. DETAILED DESCRIPTION

[0023] Example 1

[0024] A. Place Al2O3 in a tube furnace and introduce a 10% H2 / N2 reducing atmosphere for activation. Heat to 500℃ at a rate of 10℃ / min for 3h. After cooling to room temperature, unsaturated and weakly acidic AS is obtained. W Alumina support with sites (Al2O3-AS W ).

[0025] B. 0.2973 g Ni(NO3)2·6H2O and 0.2893 g Fe(NO3)3·9H2O (i.e., Ni / Fe molar ratio of 3 / 2) were dissolved in 20 mL of deionized water to prepare a mixed salt solution. The theoretical loading of active metal Ni accounted for 3.00 wt.% of the catalyst mass. 2 g of the unsaturated and weakly acidic Al2O3-AS obtained in step A was added. W The carrier was added to the mixed salt solution; the obtained uniform slurry was impregnated with an ultrasound-assisted temperature-controlled impregnation strategy, and after ultrasonication for 10 minutes at 60°C, it was stirred at 500 rpm for 6 hours until it became viscous, and dried in a constant temperature drying oven at 60°C for 24 hours to obtain Ni 2+ Fe 3+ / Al2O3-AS W Precursor.

[0026] C. Ni obtained in step A 2+ Fe 3+ / Al2O3-AS W The precursor was placed in a tube furnace and heated to 600℃ at a rate of 10℃ / min using 10% H2 / N2 for 3h with a gas flow rate of 60mL / min. After cooling to room temperature, Ni iso -AS W Ni3Fe2 / Al2O3-AS with dual-functional active sites W catalyst.

[0027] The catalyst prepared above was used in the selective hydrogenation reaction of 1,1,1,3-tetrachloropropane:

[0028] 0.3g of the above catalyst was placed in a high pressure reactor, and a 100mmol / L 1,1,1,3-tetrachloropropane ethanol solution and an acid binding agent were added. After heating to 120℃, 1.5Mpa H2 was introduced to react. 0.5mL of the working solution was analyzed every 30min. The results are shown in Table 1. Figure 5 .

[0029] Depend on Figure 5 It can be seen that it exhibits excellent dechlorination catalytic activity and selectivity. At a reaction temperature of 120°C, 1,1,1,3-tetrachloropropane is almost completely converted (95%), and the selectivity of 1,1,3-trichloropropene is 94%, which is much higher than that of the single metal Ni / Al2O3 catalyst.

[0030] Example 2

[0031] A. Place Al2O3 in a tube furnace and introduce a 10% H2 / N2 reducing atmosphere for activation treatment. Heat to 600℃ at a rate of 10℃ / min, treat for 3h, and cool to room temperature to obtain a coordination-unsaturated and weakly acidic AS. WAlumina support with sites (Al2O3-AS W ).

[0032] B. 0.1982 g Ni(NO3)2·6H2O and 0.4340 g Fe(NO3)3·9H2O (i.e., Ni / Fe molar ratio of 2 / 3) were dissolved in 20 mL of deionized water to prepare a mixed salt solution. The theoretical loading of active metal Ni accounted for 3.00 wt.% of the catalyst mass. 2 g of the unsaturated and weakly acidic Al2O3-AS obtained in step A was added. W The carrier was added to the mixed salt solution; the obtained uniform slurry was impregnated with an ultrasound-assisted temperature-controlled impregnation strategy, ultrasonicated at 60°C for 15 minutes, stirred at 500 rpm for 6 hours until it became viscous, and dried in a constant temperature drying oven at 50°C for 24 hours to obtain Ni 2+ Fe 3+ / Al2O3-AS W Precursor.

[0033] C. Ni obtained in step A 2+ Fe 3+ / Al2O3-AS W The precursor was placed in a tube furnace and heated to 600℃ at a rate of 10℃ / min using 10% H2 / N2 for 4h with a gas flow rate of 60mL / min. After cooling to room temperature, Ni iso -AS W Ni3Fe2 / Al2O3-AS with dual-functional active sites W catalyst.

[0034] The catalyst prepared above was used in the selective hydrogenation reaction of 1,1,1,3-tetrachloropropane:

[0035] 0.3 g of the above catalyst was loaded into an autoclave, and a 100 mmol / L 1,1,1,3-tetrachloropropane ethanol solution and an acid-binding agent were added. The reaction was heated to 120°C and then passed through 1.5 MPa of H2. Analysis of 0.5 mL of the working solution was performed every 30 minutes. The results showed excellent dechlorination catalytic activity and selectivity. At a reaction temperature of 120°C, the 1,1,1,3-tetrachloropropane conversion rate was 92%, and the 1,1,3-trichloropropene selectivity was 95%, far exceeding that of the monometallic Ni / Al2O3 catalyst.

[0036] Example 3

[0037] A. Place Al2O3 in a tube furnace, introduce H2 reducing atmosphere for activation treatment, heat to 600℃ at a rate of 5℃ / min, treat for 3h, and cool to room temperature to obtain unsaturated and weakly acidic AS. WAlumina support with sites (Al2O3-AS W ).

[0038] B. 0.2973 g Ni(NO3)2·6H2O and 0.1520 g Cu(NO3)2·3H2O (i.e., Ni / Cu molar ratio of 3 / 2) were dissolved in 20 mL of deionized water to prepare a mixed salt solution. The theoretical loading of active metal Ni accounted for 3.00 wt.% of the catalyst mass. 2 g of the unsaturated and weakly acidic Al2O3-AS obtained in step A was added. W The carrier was added to the mixed salt solution; the obtained uniform slurry was impregnated with an ultrasound-assisted temperature-controlled impregnation strategy, ultrasonicated at 60°C for 10 minutes, stirred at 500 rpm for 6 hours until it became viscous, and dried in a constant temperature drying oven at 50°C for 24 hours to obtain Ni 2+ Cu 2+ / Al2O3-AS W Precursor.

[0039] C. Ni obtained in step A 2+ Cu 2+ / Al2O3-AS W The precursor was placed in a tube furnace and heated to 600℃ at a rate of 10℃ / min using 10% H2 / N2 for 3h with a gas flow rate of 60mL / min. After cooling to room temperature, Ni iso -AS W Ni3Cu2 / Al2O3-AS with dual-functional active sites W catalyst.

[0040] The catalyst prepared above was used in the selective hydrogenation reaction of 1,1,1,3-tetrachloropropane:

[0041] 0.3 g of the above catalyst was loaded into an autoclave, and a 100 mmol / L 1,1,1,3-tetrachloropropane ethanol solution and an acid-binding agent were added. The reaction was heated to 120°C and then passed through 1.5 MPa of H2. Analysis of 0.5 mL of the working solution every 30 minutes revealed excellent dechlorination catalytic activity and selectivity. At a reaction temperature of 120°C, the 1,1,1,3-tetrachloropropane conversion was 96%, and the 1,1,3-trichloropropene selectivity was 93%, significantly exceeding that of the monometallic Ni / Al2O3 catalyst.

[0042] Comparative Example 1

[0043] A. Place Al2O3 in a tubular furnace, introduce N2 reducing atmosphere for activation treatment, heat to 500℃ at a rate of 15℃ / min, treat for 3h, and cool to room temperature to obtain a coordination-saturated alumina support (Al2O3).

[0044] B. 0.2973 g Ni(NO3)2·6H2O and 0.2893 g Fe(NO3)3·9H2O (i.e., Ni / Fe molar ratio of 3 / 2) were dissolved in 20 mL of deionized water to prepare a mixed salt solution. According to the theoretical loading of active metal Ni accounting for 3.00 wt.% of the catalyst mass, 2 g of the coordinated saturated Al2O3 carrier obtained in step A was added to the above mixed salt solution; the obtained uniform slurry was subjected to ultrasound-assisted-temperature controlled impregnation strategy, and after ultrasonication for 10 min at 60 ° C, it was stirred at 500 rpm for 6 h until it became viscous, and dried in a constant temperature drying oven at 50 ° C for 24 h to obtain Ni 2+ Fe 3+ / Al2O3 precursor.

[0045] C. Ni obtained in step A 2+ Fe 3+ The precursor of / Al2O3 was placed in a tube furnace and heated to 600℃ at a rate of 10℃ / min using 10% H2 / N2 for 3h with a gas flow rate of 60mL / min. After cooling to room temperature, the Ni iso Active sites of Ni3Fe2 / Al2O3 catalyst.

[0046] The catalyst prepared above was used in the selective hydrogenation reaction of 1,1,1,3-tetrachloropropane:

[0047] 0.3g of the above catalyst was placed in a high pressure reactor, and a 100mmol / L 1,1,1,3-tetrachloropropane ethanol solution and an acid binding agent were added. After heating to 120℃, 1.5Mpa H2 was introduced to react. 0.5mL of the working solution was analyzed every 30min. The results are shown in Table 1. Figure 5 .

[0048] Depend on Figure 5 It can be seen that the catalyst exhibits excellent dechlorination catalytic activity and selectivity. At a reaction temperature of 120°C, the conversion rate of 1,1,1,3-tetrachloropropane decreased with the same reaction time, while the selectivity of 1,3-trichloropropene was 87%, which is lower than that of Ni3Fe2 / Al2O3-AS. W Bifunctional catalyst.

[0049] Comparative Example 2

[0050] A. Place Al2O3 in a tube furnace and introduce a 10% H2 / N2 reducing atmosphere for activation treatment at 500°C for 3 hours. After cooling to room temperature, unsaturated and weakly acidic AS is obtained. W Alumina-supported (Al2O3-AS W ).

[0051] B. 0.2973 g Ni(NO3)2·6H2O was dissolved in 20 mL deionized water to prepare a mixed salt solution. According to the theoretical loading of active metal Ni accounting for 3.00 wt.% of the catalyst mass, 2 g of unsaturated and weakly acidic Al2O3-AS obtained in step A was added. W The carrier was added to the mixed salt solution; the obtained uniform slurry was impregnated with an ultrasound-assisted temperature-controlled impregnation strategy at 60 ° C for 20 minutes, then stirred at 500 rpm for 6 hours until it became viscous, and dried in a constant temperature drying oven at 50 ° C for 24 hours to obtain Ni 2+ / Al2O3-AS W Precursor.

[0052] C. Ni obtained in step A 2+ The precursor of / Al2O3 was placed in a tube furnace and heated to 600℃ at a rate of 10℃ / min using 10% H2 / N2 for 3h with a gas flow rate of 60mL / min. After cooling to room temperature, the Ni NPs Ni / Al2O3-AS W catalyst.

[0053] The catalyst prepared above was used in the selective hydrogenation reaction of 1,1,1,3-tetrachloropropane:

[0054] 0.3g of the above catalyst was placed in a high pressure reactor, and a 100mmol / L 1,1,1,3-tetrachloropropane ethanol solution and an acid binding agent were added. After heating to 120℃, 1.5Mpa H2 was introduced to react. 0.5mL of the working solution was analyzed every 30min. The results are shown in Table 1. Figure 5 .

[0055] Depend on Figure 5 It can be seen that the catalyst exhibits excellent dechlorination catalytic activity and selectivity. At a reaction temperature of 120°C, the conversion of 1,1,1,3-tetrachloropropane decreased (66%) with the same reaction time, and the selectivity of 1,1,3-trichloropropene was 76%, which was lower than that of Ni3Fe2 / Al2O3-AS. W Bifunctional catalyst.

[0056] Comparative Example 3

[0057] A. Place Al2O3 in a tube furnace and introduce a 10% H2 / N2 reducing atmosphere for activation. Heat to 500℃ at a rate of 15℃ / min for 3h. After cooling to room temperature, unsaturated and weakly acidic AS is obtained. W Alumina support with sites (Al2O3-AS W ).

[0058] B. 0.6622 g Ni(NO3)2·6H2O and 0.2893 g Fe(NO3)3·9H2O (i.e., Ni / Fe molar ratio of 5 / 2) were dissolved in 20 mL of deionized water to prepare a mixed salt solution. The theoretical loading of active metal Ni accounted for 5.00 wt.% of the catalyst mass. 2 g of the unsaturated and weakly acidic Al2O3-AS obtained in step A was added. W The carrier was added to the mixed salt solution; the obtained uniform slurry was impregnated with an ultrasound-assisted temperature-controlled impregnation strategy, ultrasonicated at 60°C for 10 minutes, stirred at 500 rpm for 6 hours until it became viscous, and dried in a constant temperature drying oven at 50°C for 24 hours to obtain Ni 2+ Fe 3+ / Al2O3-AS W Precursor.

[0059] C. Ni obtained in step A 2+ Fe 3+ The precursor of Ni-AS was placed in a tube furnace and heated to 600℃ at a rate of 10℃ / min using 10% H2 / N2 for 3h with a gas flow rate of 60mL / min. After cooling to room temperature, continuous Ni-AS was obtained. W Active site Ni5Fe2 / Al2O3-AS W catalyst.

[0060] The catalyst prepared above was used in the selective hydrogenation reaction of 1,1,1,3-tetrachloropropane:

[0061] 0.3 g of the above catalyst was charged into an autoclave, and a 100 mmol / L 1,1,1,3-tetrachloropropane ethanol solution and an acid-binding agent were added. The reaction was then heated to 120°C and 1.5 MPa of H₂ was introduced. Analysis of 0.5 mL of the working solution was performed every 30 minutes. The results showed excellent dechlorination catalytic activity and selectivity. At a reaction temperature of 120°C, the conversion of 1,1,1,3-tetrachloropropane was 72%, and the selectivity for 1,1,3-trichloropropene was 52%.

Claims

1. A method for preparing an isolated Ni atom-acid site bifunctional catalyst, characterized in that: Prepare according to the following specific steps: A. Place Al2O3 in a tube furnace and introduce a reducing atmosphere for activation treatment to obtain unsaturated and weakly acidic AS. W Alumina support Al2O3-AS W ; The crystalline phase of Al2O3 is one of α-Al2O3, γ-Al2O3, θ-Al2O3, and δ-Al2O3; The reducing atmosphere is one of H2 / N2, H2, CO / N2; the treatment temperature is 300-1200℃, the holding time is 2-5h, and the heating rate is 2-25℃min -1 ; B. A mixed salt solution is prepared by dissolving a soluble nickel salt and a soluble M salt in deionized water at a molar ratio of 1 to 1 / 5, and adding the alumina support obtained in step A to the mixed salt solution according to a theoretical loading amount of active metal Ni accounting for 0.03 to 5.00 wt.% of the catalyst mass; the obtained uniform slurry is stirred at 30 to 80° C. and 200 to 500 rpm for 4 to 6 hours until it becomes viscous, and dried in a constant temperature drying oven at 50 to 120° C. for 8 to 24 hours to obtain Ni 2+ M x+ / Al2O3-AS W Precursor; The soluble nickel salt is one of Ni(NO3)2·6H2O, NiCl2·6H2O, NiSO4·6H2O, and Ni(CH3COO)2·4H2O; The soluble M salt is one of Fe(NO3)3·9H2O, Fe2(SO4)3·5H2O, FeCl3·6H2O, Fe(OH)(CH3COO)2, CuSO4·5H2O, CuCl2·2H2O, Cu(NO3)2·3H2O, (CH3COO)2Cu·H2O, ZnSO4·7H2O, Zn(NO3)2·6H2O, (CH3COO)2Zn·2H2O, Co(NO3)2·6H2O, CoCl2·6H2O, and CoSO4·7H2O; C. Ni obtained in step A 2+ M x+ / Al2O3-AS W The precursor is placed in a tube furnace and heated to 400-800°C at a rate of 2-25°C / min in a reducing atmosphere for 1-5h with a gas flow rate of 40-70mL / min. After cooling to room temperature, Ni iso -AS W NiM / Al2O3-AS with dual-functional active sites W catalyst; The reducing atmosphere is one of H2 / N2, H2, and CO / N2.

2. The preparation method according to claim 1, characterized in that the reducing atmosphere in step A is one of H2 / N2 and H2; the treatment temperature is 400-600°C and the holding time is 3-4.

3. The preparation method according to claim 1, characterized in that the soluble M salt described in step A is one of Fe(NO3)3·9H2O, Cu(NO3)2·3H2O, Zn(NO3)2·6H2O, and Co(NO3)2·6H2O.

4. The preparation method according to claim 1, wherein The alumina carrier in step B is added during the ultrasound-assisted process and maintained for 10-30 minutes.

5. A method for preparing an isolated Ni atom-acid site bifunctional catalyst according to claim 1, characterized in that the reducing atmosphere in step C is one of H2 / N2 and H2; the treatment temperature is 600-700°C, and the holding time is 3-4h.

6. The preparation method according to claim 1, represented by NiM / Al2O3-AS W , wherein M represents a second metal selected from Fe, Co, Zn, and Cu; the active metal Ni accounts for 0.03 to 5.00 wt.% of the catalyst mass.

7. An isolated Ni atom-acid site bifunctional catalyst prepared by the method according to claim 1.

8. Use of the isolated Ni atom-acid site bifunctional catalyst according to claim 7, characterized in that: The catalyst was loaded into a high-pressure reactor, and a 100 mmol / L 1,1,1,3-tetrachloropropane ethanol solution and an acid binding agent were added. After heating to 120°C, 1.0-1.5 MPa H2 was introduced for reaction. The reaction liquid was taken from the reactor and detected by gas chromatograph.

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