Preparation method and application of mercaptan-modified carbon-coated nickel catalyst
By modifying the carbon-coated nickel catalyst with thiol, the problem in the existing technology that it is difficult to prevent by-products from deep hydrogenation in the catalytic hydrogenation reaction is solved, and ortho-chlorine can be obtained with high selectivity at a lower temperature and in a short time. aniline and maintains high activity during long-term reactions.
Patent Information
- Application Number
- CN202411447750.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-16
- Publication Date
- 2025-01-21
AI Technical Summary
The prior art is difficult to prevent deep hydrogenation from producing by-products in catalyzed orthochloronitrobenzene hydrogenation reaction, and the activity of the catalyst decreases over a long reaction time.
The nickel covering catalyst is used to modify the carbon alcohol, and the carbon nickel covered catalyst is formed by mixing nickel nitrate and citric acid. Essence
At lower reaction temperatures and shorter reaction times, the catalyst has extremely high selectivity for the hydrogenation of o-chloronitrobenzene, which can effectively prevent the formation of by-products during deep hydrogenation and maintain high selectivity and stability during long-term reactions. stability.
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Figure CN119327460A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of catalytic hydrogenation, and specifically relates to a preparation method and application of a thiol-modified carbon-coated nickel catalyst. Background Art
[0002] As an important organic intermediate, o-chloroaniline is widely used in dyes, medicines, pesticides and other fields. It is mainly obtained by hydrogenation of o-chloronitrobenzene. Catalytic hydrogenation of o-chloronitrobenzene is a cascade reaction, such as Figure 1 As shown in the figure, the key to this technology is to select suitable catalysts and reaction conditions to achieve efficient and highly selective generation of the intermediate product o-chloroaniline, and to prevent deep hydrogenation and dechlorination to generate aniline during the reaction. Commonly used catalysts include palladium, platinum and nickel-based catalysts, which usually need to be modified to have high selectivity for o-chloroaniline. Among them, the modification method by regulating the electronic structure of the catalyst metal is a research direction that many scholars are keen on. However, this modification method will still produce by-products when working for a long reaction time. Even in the case of complete conversion, the long reaction time is unnecessary in actual industrial production.
[0003] Sulfur is an element containing lone pairs of electrons, which makes it have a strong coordination and complexing effect on metals, causing the catalyst to be poisoned and lose its activity. Mercaptan is a molecule containing a thiol group (-SH) at the end of an alkane chain. Generally speaking, the thiol group of mercaptan can be strongly adsorbed on the metal surface of the catalyst, while the alkyl chain stands upright on the metal surface of the catalyst. Many scholars have found that after using mercaptan to modify the catalyst, the mercaptan molecules only exist on the metal surface of the catalyst, and the sulfur element will not penetrate into the metal particles to cause phase transition and deactivation. In addition, the adsorbed mercaptan regulates the adsorption configuration of the adsorbed substance due to the presence of the alkyl chain.
[0004] In the present invention, a high hydrogenation activity catalyst is modified by using mercaptan molecules and then applied to the reaction of selectively hydrogenating o-chloronitrobenzene to obtain o-chloroaniline. The presence of mercaptan molecules on the catalyst surface regulates the adsorption configuration of o-chloroaniline, so that the benzene ring or chlorine group will not be adsorbed on the catalyst, but the nitro group will be preferentially and only adsorbed. The purpose of the tandem reaction is to terminate at the intermediate product o-chloroaniline. Summary of the invention
[0005] The purpose of the present invention is to overcome the technical problem of selectively hydrogenating o-chloronitrobenzene to obtain o-chloroaniline and preventing the generation of by-products during deep hydrogenation, and to provide a method for preparing a thiol-modified carbon-coated nickel catalyst. The synthesized catalyst of the present invention can hydrogenate o-chloronitrobenzene to obtain o-chloroaniline with extremely high selectivity at a lower reaction temperature and a shorter reaction time, and it is confirmed through long-term reaction experiments that o-chloroaniline will not be deeply hydrogenated to aniline.
[0006] Another object of the present invention is to provide a thiol-modified carbon-coated nickel catalyst.
[0007] Another object of the present invention is to provide an application of a mercaptan-modified carbon-coated nickel catalyst in catalyzing the selective hydrogenation of o-chloronitrobenzene to synthesize o-chloroaniline.
[0008] To achieve the above purpose, the technical solution adopted by the present invention is as follows:
[0009] A method for preparing a thiol-modified carbon-coated nickel catalyst comprises the following steps in sequence:
[0010] S1. nickel nitrate and citric acid are mixed uniformly in a molar ratio of 1:1 to 3 to obtain a precursor;
[0011] S2. The precursor obtained in step S1 is completely pyrolyzed in a nitrogen atmosphere at a temperature of 400 to 650° C. to obtain a carbon-coated nickel Ni@C catalyst;
[0012] S3. The carbon-coated nickel Ni@C catalyst obtained in step S2 is immersed in a thiol-ethanol solution and subjected to a hydrothermal reaction at 80-140° C. for 3 to 24 h for thiol modification to obtain a thiol-modified carbon-coated nickel catalyst;
[0013] In S3, when the modified carbon-coated nickel Ni@C catalyst is 0.3 g, the amount of thiol used is 0.5 to 213.3 mol.
[0014] Furthermore, in the above-mentioned method for preparing the thiol-modified carbon-coated nickel catalyst, the molar ratio of nickel nitrate to citric acid in step S1 is 1:2.
[0015] Furthermore, in the above-mentioned method for preparing the thiol-modified carbon-coated nickel catalyst, the pyrolysis temperature in step S2 is 550°C.
[0016] Furthermore, in the above-mentioned method for preparing the thiol-modified carbon-coated nickel catalyst, the thiol in step S3 is one of propyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, and n-dodecyl mercaptan.
[0017] Furthermore, in the above-mentioned method for preparing the thiol-modified carbon-coated nickel catalyst, in step S3, when the modified carbon-coated nickel Ni@C catalyst is 0.3 g, the amount of thiol used is 118.5 mol.
[0018] Furthermore, in the above-mentioned method for preparing the thiol-modified carbon-coated nickel catalyst, the hydrothermal temperature in step S3 is 120°C.
[0019] Furthermore, in the above-mentioned method for preparing the thiol-modified carbon-coated nickel catalyst, the hydrothermal time in step S3 is 12 hours.
[0020] The second technical solution provided by the present invention is a method for preparing a thiol-modified carbon-coated nickel catalyst, which is obtained by the preparation method described in the first technical solution.
[0021] The third technical solution provided by the present invention is to use the above-mentioned thiol-modified carbon-coated nickel catalyst in catalyzing the selective hydrogenation of o-chloronitrobenzene to synthesize o-chloroaniline.
[0022] The third technical scheme provided by the present invention is a method for synthesizing o-chloroaniline by selective hydrogenation of o-chloronitrobenzene, wherein a thiol-modified carbon-coated nickel catalyst, o-chloronitrobenzene, and ethanol are placed in a batch reactor, reacted at 1-3 MPa H2 and 80-120°C for 2-16 hours, and the product finally obtained is tested and analyzed by gas chromatography;
[0023] The mass ratio of the mercaptan-modified carbon-coated nickel catalyst, o-chloronitrobenzene and ethanol is 0.1:0.5:10.
[0024] Further, the selective hydrogenation of o-chloronitrobenzene comprises the following steps:
[0025] The above-mentioned 0.1 g of thiol-modified carbon-coated nickel catalyst, 0.5 g of o-chloronitrobenzene, and 10 g of ethanol were placed in a 50 mL intermittent reactor, and reacted at 2 MPa H2 and 100°C for 8 h. The final product was tested and analyzed using gas chromatography (GC).
[0026] The beneficial effects of the present invention are:
[0027] (1) The synthesized catalyst of the present invention can hydrogenate o-chloronitrobenzene to obtain o-chloroaniline with extremely high selectivity at a lower reaction temperature and a shorter reaction time.
[0028] (2) The catalyst synthesized by the present invention can carry out the hydrogenation reaction of o-chloronitrobenzene under a longer reaction time and still has a high selectivity for o-chloroaniline, and it is difficult to undergo deep hydrogenation to generate aniline.
[0029] (3) The synthesized catalyst of the present invention has excellent stability and can undergo multiple cycle reactions. BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Figure 1 This is the reaction pathway for the hydrogenation of o-chloronitrobenzene;
[0031] Figure 2 This is the X-ray powder diffraction (XRD) pattern of the thiol-modified carbon-coated nickel catalyst prepared in Example 1;
[0032] Figure 3 This is a transmission electron microscope (TEM) image of the thiol-modified carbon-coated nickel catalyst prepared in Example 1;
[0033] Figure 4 This is the GC graph of the mercaptan-modified carbon-coated nickel catalyst prepared in Example 1 after the hydrogenation reaction of o-chloronitrobenzene. DETAILED DESCRIPTION
[0034] The present invention is further described below in conjunction with the accompanying drawings and specific examples, which do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.
[0035] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
[0036] Example 1
[0037] S1. nickel nitrate and citric acid were dissolved in water in a molar ratio of 1:2, and the solvent was removed by heating and stirring at 80°C to obtain a precursor;
[0038] S2. The precursor obtained in step S1 is completely pyrolyzed in a nitrogen atmosphere at 550° C. to obtain a carbon-coated nickel Ni@C catalyst;
[0039] S3. The carbon-coated nickel Ni@C catalyst obtained in step S2 is immersed in a thiol-ethanol solution, wherein the catalyst is 0.3 g, the molar amount of n-octyl mercaptan is 118.5 mol, and the ethanol is 40 mL, and a thiol-modified hydrothermal reaction is carried out at 120° C. for 12 h.
[0040] Example 2
[0041] The difference from Example 1 is that in step S1, the molar ratio of nickel nitrate to citric acid in this example is 1:1, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0042] Example 3
[0043] The difference from Example 1 is that in step S1, the molar ratio of nickel nitrate to citric acid in this example is 1:3, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0044] Example 4
[0045] The difference from Example 1 is that in step S2, the pyrolysis temperature in this embodiment is 400°C, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0046] Example 5
[0047] The difference from Example 1 is that in step S2, the pyrolysis temperature in this embodiment is 650°C, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0048] Example 6
[0049] The difference from Example 1 is that in step S3, the thiol used in this example is propylthiol, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0050] Example 7
[0051] The difference from Example 1 is that in step S3, the mercaptan used in this example is n-butyl mercaptan, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0052] Example 8
[0053] The difference from Example 1 is that in step S3, the thiol used in this example is n-dodecyl mercaptan, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0054] Example 9
[0055] The difference from Example 1 is that in step S3, the amount of n-octyl mercaptan used in this example is 0.5 mol, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0056] Example 10
[0057] The difference from Example 1 is that in step S3, the amount of n-octyl mercaptan used in this example is 1.2 mol, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0058] Embodiment 11
[0059] The difference from Example 1 is that in step S3, the amount of n-octyl mercaptan used in this example is 4.7 mol, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0060] Example 12
[0061] The difference from Example 1 is that in step S3, the amount of n-octyl mercaptan used in this example is 23.7 mol, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0062] Embodiment 13
[0063] The difference from Example 1 is that in step S3, the amount of n-octyl mercaptan used in this example is 213.3 mol, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0064] Embodiment 14
[0065] The difference from Example 1 is that in step S3, the hydrothermal modification temperature in this embodiment is 80° C., and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0066] Embodiment 15
[0067] The difference from Example 1 is that in step S3, the hydrothermal modification temperature in this embodiment is 120° C., and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0068] Example 16
[0069] The difference from Example 1 is that in step S3, the hydrothermal modification temperature in this embodiment is 130° C., and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0070] Embodiment 17
[0071] The difference from Example 1 is that in step S3, the hydrothermal modification temperature in this embodiment is 140° C., and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0072] Embodiment 18
[0073] The difference from Example 1 is that in step S3, the hydrothermal modification time in this embodiment is 3 hours, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0074] Embodiment 19
[0075] The difference from Example 1 is that in step S3, the hydrothermal modification time in this embodiment is 24 hours, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0076] Comparative Example 1
[0077] The difference from Example 1 is that in step S1, the molar ratio of nickel nitrate to citric acid in this example is 1:0.5, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0078] Comparative Example 2
[0079] The difference from Example 1 is that in step S2, the pyrolysis temperature in this embodiment is 300°C, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0080] Comparative Example 3
[0081] The difference from Example 1 is that in step S3, no thiol is used for modification in this example, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0082] Comparative Example 4
[0083] The difference from Example 1 is that in step S3, the amount of n-octyl mercaptan used in this example is 0.2 mol, and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0084] Comparative Example 5
[0085] The difference from Example 1 is that in step S3, the hydrothermal modification temperature in this embodiment is 50° C., and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0086] Comparative Example 6
[0087] The difference from Example 1 is that in step S3, the hydrothermal modification temperature in this embodiment is 180° C., and the conditions, reagents and amounts of the remaining steps are consistent with those in Example 1.
[0088] Characterization Test
[0089] The present application uses the thiol-modified carbon-coated nickel catalyst prepared in Example 1 as an example to perform performance tests, and the thiol-modified carbon-coated nickel catalysts prepared in other examples have the same effect.
[0090] X-ray powder diffraction test: The thiol-modified carbon-coated nickel catalyst obtained in Example 1 was subjected to X-ray powder diffraction (XRD) test. The results are as follows: Figure 1 As shown: the thiol-modified carbon-coated catalyst obtained in Example 1 has a typical nickel metal diffraction peak, and the XRD spectra of the catalysts described in Examples 2 to 19 are basically consistent with that in Example 1.
[0091] Transmission electron microscopy test: The thiol-modified carbon-coated nickel catalyst prepared in Example 1 was subjected to transmission electron microscopy (TEM) test. Figure 2 As shown, the illustration is a particle size distribution diagram: it can be observed that the catalyst contains multiple extremely small nickel nanoparticles with an average particle size of 9.81nm. The extremely small particle size gives the catalyst good catalytic activity; and it can be observed that the nickel nanoparticles are surrounded by a carbon layer, which can stabilize the size of the metal so that it will not grow during the reaction and maintain the high dispersion characteristics of the catalyst.
[0092] Inductively coupled plasma test: The thiol-modified carbon-coated nickel catalyst prepared in Example 1 was subjected to inductively coupled plasma (ICP) test. The results are shown in Table 1: It can be seen that the nickel content of the catalyst is 59.71 wt %. Such a high loading and high dispersibility ensure the catalytic activity of the catalyst.
[0093] Elemental analysis test: The mercaptan-modified carbon-coated nickel catalyst prepared in Example 1 was subjected to transmission electron microscopy (TEM) test. The results are shown in Table 1: It can be seen that the sulfur content of the catalyst after mercaptan modification is 7.12 wt %, proving that mercaptan is adsorbed on the catalyst surface.
[0094] Table 1 Catalyst element content
[0095] Ni / wt% N / wt% C / wt% H / wt% S / wt% O / wt% 59.71 0.47 24.92 2.94 7.12 4.83
[0096] Application Example 1 Selective hydrogenation of o-chloronitrobenzene to o-chloroaniline catalyzed by mercaptan-modified carbon-coated nickel catalyst
[0097] The reaction pathway is shown in Figure 1 0.1 g of the thiol-modified carbon-coated nickel catalyst described in any one of Examples 1-19, 0.5 g of o-chloronitrobenzene, and 10 g of ethanol were placed in a 50 mL batch reactor, and the reaction was carried out at 2 MPa H2 and 100°C for 8 h. The final product was tested and analyzed using gas chromatography (GC).
[0098] Table 2 Selective hydrogenation of o-chloronitrobenzene to o-chloroaniline catalyzed by different catalysts
[0099]
[0100]
[0101] As can be seen from Table 2, the catalysts provided in Examples 1 to 8 have excellent selectivity for o-chloroaniline in the o-chloronitrobenzene hydrogenation reaction after being modified with mercaptan using different nickel nitrate / citric acid ratios, pyrolysis temperatures, and mercaptan types. The catalyst synthesized in Comparative Example 1 has a low conversion rate due to the large nickel metal particles and the small exposed active area. The catalyst synthesized in Comparative Example 2 has a low pyrolysis temperature and a low nickel crystallinity, resulting in a low conversion rate. It can be seen from Examples 9 to 13 and Comparative Examples 3 to 4 that the catalyst has improved selectivity for o-chloronitrobenzene after being modified with mercaptan. When the amount of mercaptan is increased to 0.5 mol, almost full yield can be achieved, and under the modification conditions of extremely high mercaptan concentrations, mercaptan does not poison the catalyst, indicating that mercaptan only modifies the catalyst surface, and the modified catalyst still has extremely high conversion rate and selectivity. It can be seen from Examples 14 to 17 and Comparative Examples 5 to 6 that the catalysts exhibited good conversion and selectivity at a modification temperature of 80 to 140°C, with 120°C being the best. At a modification temperature of 50°C, the mercaptan adsorbed on the catalyst surface was not firm and fell off during the reaction, and the adsorption configuration could not be regulated, resulting in low selectivity. At a high modification temperature of 180°C, the mercaptan poisoned the catalyst, resulting in an extremely low conversion rate. It can be seen that the main factor that poisons the catalyst is temperature rather than the concentration of mercaptan. Examples 18 to 19 show that the catalysts can exhibit good conversion and selectivity at a modification time of 3 to 24 hours.
[0102] Application Example 20
[0103] 0.1 g of the thiol-modified carbon-coated nickel catalyst described in Example 1, 0.5 g of o-chloronitrobenzene, and 10 g of ethanol were placed in a 50 mL batch reactor, and reacted at 2 MPa H2 and 100°C for 2 h. The final product was tested and analyzed using gas chromatography (GC).
[0104] Table 3 Mercaptan-modified carbon-coated nickel catalyst for short-term catalytic hydrogenation of o-chloronitrobenzene
[0105] Reaction time / h Conversion rate / % Selectivity / % 2 100 99.95
[0106] It can be seen from Application Example 20 that the catalyst modified with mercaptan can completely hydrogenate o-chloronitrobenzene within 2 h and has extremely high selectivity for o-chloroaniline, which shows that the catalyst has an extremely high space-time yield.
[0107] Application Example 21
[0108] 0.1 g of the thiol-modified carbon-coated nickel catalyst described in Example 1, 0.5 g of o-chloronitrobenzene, and 10 g of ethanol were placed in a 50 mL batch reactor, and reacted at 2 MPa H2 and 100°C for 16 h. The final product was tested and analyzed using gas chromatography (GC).
[0109] Table 4 Long-term catalytic hydrogenation of o-chloronitrobenzene by mercaptan-modified carbon-coated nickel catalyst
[0110] Reaction time / h Conversion rate / % Selectivity / % 16 100 99.92
[0111] It can be seen from Application Example 21 that the mercaptan-modified carbon-coated nickel catalyst still has extremely high selectivity for o-chloroaniline after the 16h hydrogenation reaction of o-chloronitrobenzene. During this cascade reaction, the catalyst only reacts to the target product o-chloroaniline and terminates, and will not further hydrogenate and dechlorinate to produce the by-product aniline.
[0112] Cycle experiment
[0113] 0.1 g of the thiol-modified carbon-coated nickel catalyst of Example 1, 0.5 g of o-chloronitrobenzene, and 10 g of ethanol were placed in a 50 mL batch reactor and reacted at 2 MPa H2 and 100°C for 2 h. The same catalyst was recycled 3 times, and the product obtained each time was tested and analyzed using gas chromatography (GC).
[0114] Table 5 Example 1 Catalyst catalyzed selective hydrogenation of o-chloronitrobenzene to o-chloroaniline cycle experiment
[0115] Cycle times Conversion rate / % Selectivity / % 1 100 99.95 2 99.87 99.91 3 99.87 99.91
[0116] It can be seen from the cycle experiment in Table 5 that the catalyst can also completely and selectively convert o-chloronitrobenzene into o-chloronitrobenzene within 2 h, and still maintains good conversion rate and selectivity after 3 cycles.
[0117] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.
Claims
1. A method for preparing a thiol-modified carbon-coated nickel catalyst, characterized in that: The steps are as follows: S1. nickel nitrate and citric acid are mixed uniformly in a molar ratio of 1:1 to 3 to obtain a precursor; S2. The precursor obtained in step S1 is completely pyrolyzed in a nitrogen atmosphere at a temperature of 400 to 650° C. to obtain a carbon-coated nickel Ni@C catalyst; S3. The carbon-coated nickel Ni@C catalyst obtained in step S2 is immersed in a thiol-ethanol solution, and subjected to a hydrothermal reaction at 80-140° C. for 3 to 24 hours for thiol modification to obtain a thiol-modified carbon-coated nickel catalyst; In S3, when the modified carbon-coated nickel Ni@C catalyst is 0.3 g, the amount of thiol used is 0.5 to 213.3 mol.
2. The method for preparing the thiol-modified carbon-coated nickel catalyst according to claim 1, characterized in that: The molar ratio of nickel nitrate to citric acid in step S1 is 1:
2.
3. The method for preparing the thiol-modified carbon-coated nickel catalyst according to claim 1, characterized in that: The pyrolysis temperature in step S2 is 550°C.
4. The method for preparing the thiol-modified carbon-coated nickel catalyst according to claim 1, characterized in that: The mercaptan in step S3 is one of propyl mercaptan, n-butyl mercaptan, n-octyl mercaptan and n-dodecyl mercaptan.
5. The method for preparing the thiol-modified carbon-coated nickel catalyst according to claim 1, characterized in that: In step S3: when the amount of the modified carbon-coated nickel Ni@C catalyst is 0.3 g, the amount of mercaptan used is 118.5 mol.
6. The method for preparing the thiol-modified carbon-coated nickel catalyst according to claim 1, characterized in that: The hydrothermal temperature in step S3 is 120°C.
7. The method for preparing a thiol-modified carbon-coated nickel catalyst according to claim 1, characterized in that: The hydrothermal time in step S3 is 12 hours.
8. A method for preparing a thiol-modified carbon-coated nickel catalyst, characterized in that: Obtained by the preparation method according to any one of claims 1 to 7.
9. Use of the mercaptan-modified carbon-coated nickel catalyst according to claim 8 in catalyzing the selective hydrogenation of o-chloronitrobenzene to synthesize o-chloroaniline.
10. A method for synthesizing o-chloroaniline by selective hydrogenation of o-chloronitrobenzene, comprising placing the mercaptan-modified carbon-coated nickel catalyst according to claim 7, o-chloronitrobenzene, and ethanol in a batch reactor, reacting for 2-16 hours at 1-3 MPa H2 and 80-120°C, and finally obtaining a product for testing and analysis using gas chromatography; The mass ratio of the mercaptan-modified carbon-coated nickel catalyst, o-chloronitrobenzene and ethanol is 0.1:0.5:10.