A nickel-based catalyst for olefin hydroformylation reaction, its preparation method and application

Abstract

The present application relates to the technical field of catalyst, in particular to a nickel-based catalyst for olefin hydroformylation reaction, the catalyst comprises an active ingredient and a C carrier, the active ingredient comprises Ni and an auxiliary agent, the active ingredient is loaded on the C carrier, the auxiliary agent is selected from alkali metal and / or alkaline earth metal, the content of the Ni is 0.2-20 wt% based on the total mass of the catalyst, and the content of the auxiliary agent is 0.1-5 wt%. The catalyst has the advantages of low cost, relatively simple preparation process and potential for industrial production application; the catalyst can generate activity phase transition in a relatively short time, thereby effectively improving the overall olefin conversion rate and the selectivity of the product, reducing the occurrence of side reactions; and effectively realizing the preparation of propionaldehyde and propanol by ethylene hydroformylation.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a nickel-based catalyst for the hydroformylation reaction of olefins, its preparation method, and its application. Background Technology

[0002] The hydroformylation of olefins is a reaction that converts olefins, hydrogen, and carbon monoxide into aldehydes with one more carbon atom, and it is one of the most important olefin upscaling reactions. How to utilize raw olefins more efficiently, improve catalyst activity and stability, and reduce costs while increasing efficiency are important research topics in hydroformylation catalysis. Currently, homogeneous Rh-based hydroformylation catalysts are the most widely used in industry, possessing relatively high reactivity. However, homogeneous Rh catalysts typically face problems such as high cost and difficulty in recovery. Therefore, the development of heterogeneous non-Rh-based hydroformylation catalysts has attracted widespread attention. The active metals of reported heterogeneous hydroformylation catalysts are often Rh, Ru, and Co, but these metals are still relatively expensive. Therefore, if Ni, which is relatively cheaper, could be used as the active metal, the catalyst cost could be significantly reduced.

[0003] Ni, as a group VIII metal, has a similar electronic structure to Rh, Ru, and Co. However, general studies have shown that its hydroformylation catalytic activity is low. This is usually closely related to the electronic and structural properties of the catalyst itself, as well as the reaction conditions in the actual application process.

[0004] Therefore, it is necessary to develop a low-cost, highly active nickel-based catalyst for the hydroformylation of olefins. Summary of the Invention

[0005] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a nickel-based catalyst for the hydroformylation reaction of olefins, its preparation method and application, so as to solve the problems of high cost of noble metal catalysts and low activity of nickel-based catalysts in the prior art.

[0006] To achieve the above and other related objectives, the first aspect of the present invention provides a nickel-based catalyst for the hydroformylation reaction of olefins, the catalyst comprising an active component and a C support, the active component comprising Ni and an auxiliary agent, the active component being supported on the C support, the auxiliary agent being selected from alkali metals and / or alkaline earth metals, and the content of Ni being 0.2 to 20 wt% and the content of the auxiliary agent being 0.1 to 5 wt% based on the total mass of the catalyst.

[0007] The Ni content can be 0.2~2 wt%, 2~4 wt%, 4~6 wt%, 6~8 wt%, 8~10 wt%, 10~12 wt%, 12~14 wt%, 14~16 wt%, 16~18 wt%, or 18~20 wt%. If the Ni content is higher than 20 wt%, the reducing hydrogenation capacity will be too strong, resulting in a significant increase in the selectivity of ethane in the product; if the Ni content is lower than 0.2 wt%, the number of active sites will be less, leading to a lower overall ethylene conversion rate and product yield.

[0008] The content of the aforementioned adjuvant can be 0.1~0.5 wt%, 0.5~1 wt%, 1~1.5 wt%, 1.5~2 wt%, 2~2.5 wt%, 2.5~3 wt%, 3~3.5 wt%, 3.5~4 wt%, 4~4.5 wt%, or 4.5~5 wt%.

[0009] Preferably, the auxiliary agent is selected from one or more of Li, Na, K, Rb, Cs, Mg, and Ba.

[0010] Preferably, the C carrier is selected from one or more of activated carbon, coconut shell carbon, carbon nitride, and graphite powder. The inventors of this application have found through extensive experiments that other conventional oxide carriers (such as silicon oxide, zirconium oxide, titanium oxide, and alumina) cannot achieve the technical effects of the solution described in this application.

[0011] Preferably, the specific surface area of ​​the C-carrier is 600–1200 m². 2 / g. For example, it can be 600~690 m. 2 / g、690~800m 2 / g, 800~900 m 2 / g, 900~1000 m 2 / g, 1000~1100 m 2 / g, 1100~1200 m 2 / g.

[0012] Preferably, the average particle size of the C-carrier is 0.1~0.4 mm. For example, it can be 0.1~0.15 mm, 0.15~0.2 mm, 0.2~0.25 mm, 0.25~0.3 mm, 0.3~0.35 mm, or 0.35~0.4 mm.

[0013] The second aspect of this application discloses a method for preparing the catalyst as described above, the method comprising the following steps: impregnating a C support with a mixed aqueous solution of Ni and a soluble salt corresponding to an auxiliary agent, followed by drying and calcination.

[0014] Preferably, the impregnation is an equal-volume impregnation.

[0015] Preferably, the immersion is carried out in a constant temperature water bath.

[0016] More preferably, the temperature of the constant temperature water bath is 50~80℃. For example, it can be 50~60℃, 60~70℃, or 70~80℃.

[0017] Preferably, the soluble salt corresponding to Ni and the auxiliary agent is selected from one or more of nitrates, chlorides, and sulfates.

[0018] More preferably, the soluble salt corresponding to Ni and the additive is selected from nitrates. Nitrates are easily decomposed during subsequent drying and calcination and are less likely to remain in the catalyst.

[0019] Preferably, the molar ratio of Ni to the additive in the mixed aqueous solution is 1:2 to 20. For example, it can be 1:2 to 4, 1:4 to 5, 1:5 to 6, 1:6 to 8, 1:8 to 10, 1:10 to 12, 1:12 to 14, 1:14 to 18, or 1:18 to 20.

[0020] Preferably, the concentration of Ni and the soluble salt corresponding to the auxiliary agent in the mixed aqueous solution is 0.2~2 g / mL. For example, it can be 0.2~0.4 g / mL, 0.4~0.6 g / mL, 0.6~0.8 g / mL, 0.8~1.0 g / mL, 1.0~1.2 g / mL, 1.2~1.4 g / mL, 1.4~1.6 g / mL, or 1.6~2.0 g / mL.

[0021] Preferably, the drying is carried out in a vacuum environment.

[0022] Preferably, the drying temperature is 50~200℃. For example, it can be 50~100℃, 100~150℃, or 150~200℃.

[0023] Preferably, the drying time is 5-20 hours. For example, it can be 5-10 hours, 10-15 hours, or 15-20 hours.

[0024] Preferably, the calcination temperature is 200~400℃. For example, it can be 200~250℃, 250~300℃, 300~350℃, or 350~400℃.

[0025] Preferably, the roasting time is 4-6 hours. For example, it can be 4-4.5 hours, 4.5-5 hours, 5-5.5 hours, or 5.5-6 hours.

[0026] The third aspect of this application discloses the use of the above-mentioned catalyst in the catalytic hydroformylation reaction of olefins.

[0027] Preferably, the selectivity of the catalyst for ethane in the catalytic hydroformylation reaction of olefins is at most 60%, more preferably 25-60%. For example, it can be 25-30%, 30-35%, 35-40%, 40-45%, 45-50%, or 50-60%.

[0028] Preferably, the selectivity of the catalyst in catalyzing the hydroformylation of olefins with 3-pentanone is at most 4%, more preferably 0-3.8%. For example, it can be 0-1%, 1-2%, 2-3%, or 3-3.8%.

[0029] Preferably, the catalyst exhibits a combined selectivity of at least 40% for acetone and propanol in the catalytic hydroformylation reaction of olefins, more preferably 40-75%. Examples of selectivity values ​​include 40-45%, 45-50%, 50-55%, 55-60%, 60-70%, and 70-75%.

[0030] The fourth aspect of this application discloses a method for catalyzing the hydroformylation reaction of olefins using the above-described catalyst.

[0031] Preferably, the reaction further includes a step of reducing the catalyst.

[0032] More preferably, the atmosphere for the reduction treatment is selected from one or more of a mixture of argon and hydrogen, or pure hydrogen.

[0033] More preferably, the volume ratio of H2 to Ar in the atmosphere is 1:9~99. For example, it can be 1:9~15, 1:15~20, 1:20~30, 1:30~40, 1:40~50, 1:50~60, 1:60~70, 1:70~80, 1:80~90, or 1:90~99.

[0034] More preferably, the reduction treatment time is 3 to 10 hours. For example, it can be 3 to 5 hours, 5 to 7 hours, 7 to 9 hours, or 9 to 10 hours.

[0035] More preferably, the temperature of the reduction treatment is 120~650℃. For example, it can be 120~200℃, 200~300℃, 300~400℃, 400~500℃, 500~600℃, or 600~650℃.

[0036] More preferably, the reduction process includes three heating programs: the first heating program has a temperature of 150℃-180℃ and a reduction time of 1-3 h, with a reduction atmosphere of a mixture of H2 and Ar; the second heating program has a temperature of 370℃-410℃ and a reduction time of 1-5 h, with a reduction atmosphere of H2; and the third heating program has a temperature of 580℃-600℃ and a reduction time of 1-3 h, with a reduction atmosphere of H2.

[0037] More preferably, the pressure of the reduction treatment is 0~2MPa.

[0038] More preferably, the space velocity of the reduction process is 6000~8000 h⁻¹. -1 For example, it can be 6000~7000 h. -1 7000~8000 h -1 .

[0039] Preferably, the reaction gas comprises ethylene, CO and H2, with a volume ratio of ethylene:CO:H2 of 1:(0.5~2):(0.5~2).

[0040] More preferably, the proportion of ethylene in the reaction gas is 20% to 50%. For example, it can be 20% to 25%, 25% to 30%, 30% to 35%, 35% to 40%, 40% to 45%, or 45% to 50%. If the proportion of ethylene is higher than 50%, the partial pressure of H2 and CO in the reaction system will be too high, which is not conducive to the occurrence of hydroformylation reaction, thus causing the reaction to tend to proceed to the process of hydrogenation reduction to produce ethane. If the proportion of ethylene is lower than 20%, the overall conversion rate of ethylene will decrease significantly, the yield will decrease, and the feed gas will be wasted.

[0041] Preferably, the reaction pressure is 2-4 MPa.

[0042] Preferably, the reaction temperature is 180~200 °C.

[0043] Preferably, the reaction time is 15-20 h.

[0044] In this application, the olefin hydroformylation reaction is the hydroformylation of ethylene to propanol and propanal. The reaction of ethylene hydroformylation to propanol and propanal is carried out in a batch reactor, and space velocity is generally not considered.

[0045] Compared with the prior art, the present invention has the following beneficial effects:

[0046] 1) This application uses nickel as the active metal, which greatly reduces the cost of the catalyst and can effectively realize the hydroformylation of ethylene to prepare propionaldehyde and propanol.

[0047] 2) This invention improves the dispersion of Ni and changes the average valence state of Ni particles on the surface by adjusting the precursor treatment method, reducing atmosphere, and reducing temperature in the catalyst preparation process. This improves the hydroformylation activity and reduces the hydrogenation side reaction ability, thus significantly reducing the side reaction occurrence ability and showing potential for industrial production application.

[0048] 3) The catalyst described in this invention can undergo an active phase transformation in a relatively short time, thereby effectively improving the overall olefin conversion rate and product selectivity, and reducing the occurrence of side reactions. Detailed Implementation

[0049] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0050] Before further describing specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terminology used in the embodiments of the present invention is for describing specific embodiments and not for limiting the scope of protection of the present invention. Test methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the respective manufacturers.

[0051] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, apparatus, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, apparatus, and materials similar to or equivalent to those described, apparatus, and materials in the embodiments of this invention may be used to implement the present invention.

[0052] This application provides a nickel-based catalyst for the hydroformylation of olefins, its preparation method, and its application, to address the problems of high cost of precious metal catalysts and low activity of nickel-based catalysts in the prior art. The catalyst has low cost, a relatively simple preparation process, and potential for industrial production. The catalyst can undergo an active phase transition in a relatively short time, thereby effectively improving the overall olefin conversion rate and product selectivity, and reducing side reactions; it effectively achieves the hydroformylation of ethylene to prepare propionaldehyde and propanol.

[0053] The reaction results of the catalyst described in the embodiments of this application were obtained by the following method:

[0054] 1) Use gas chromatography (Agilent 8860B) to analyze the types and contents of various components contained in the product;

[0055] 2) The C2H4 conversion rate is calculated using the following formula:

[0056] C2H4 conversion (%) = ,

[0057] Where C2H4inlet and C2H4outlet represent the number of moles of C2H4 before and after the reaction, respectively.

[0058] 3) The formula for calculating product selectivity is:

[0059]

[0060] Where n(products) is the amount of substance of the corresponding product, and n(total product) is the sum of the amounts of all substances in the product.

[0061] The specific surface area of ​​the actual carrier in the following embodiments of this application was obtained by testing with a JW-BK200C instrument, and the particle size was obtained by statistical analysis of STEM characterization results.

[0062] It should be noted that the amount of catalyst used can be adjusted according to the specific catalyst's catalytic effectiveness, reaction conditions, ease of operation and economy, as well as long-term operational stability.

[0063] Example 1

[0064] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, the method comprising the following steps:

[0065] 1) Mix 0.01 g / mL NaNO3 solution and 0.05 g / mL Ni(NO3)2 solution at a Na:Ni ratio of 1:5. Under constant temperature water bath conditions of 60 ℃, slowly add the precursor solution dropwise to pre-dried and dehydrated activated carbon carrier powder using a normal pressure dropping funnel, and stir thoroughly to impregnate the powder by equal volume until fully loaded; the activated carbon carrier has an average surface area of ​​800 m². 2 / g, with an average particle size of 0.2 mm.

[0066] 2) The impregnated powder was transferred to a vacuum drying oven for processing. After being evacuated, it was heated to 200 °C and dried for 24 hours. The calcined powder was then transferred to a tube furnace and calcined at 400 °C for 4 hours under inert gas protection, and then cooled to room temperature.

[0067] 3) Then, the temperature is programmed to 150 ℃ at a rate of 2 ℃ / min, and reduced with a 1% H2 / 99% Ar mixed gas for 2 h; then the temperature is programmed to 400 ℃ at a rate of 2 ℃ / min, and then pure H2 is used for 3 h; finally, the temperature is programmed to 600 ℃ at a rate of 5 ℃ / min and maintained for 1 h, and then cooled and passivated for later use.

[0068] 200 mg of catalyst was transferred to a high-pressure reactor. Synthesis gas with 25% ethylene and a 1:1 volume ratio of 75% CO and H2 was introduced to a mixed reaction gas pressure of 4 MPa. The reaction temperature was set to 200 °C. After 15 h of reaction, the types and contents of various components in the product were analyzed by Agilent 8860B chromatography, and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0069] Example 2

[0070] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, the method comprising the following steps:

[0071] 1) Mix 0.01 g / mL KNO3 solution and 0.05 g / mL Ni(NO3)2 solution at a mass ratio of K:Ni = 1:5. Under constant temperature water bath conditions of 60 ℃, slowly add the precursor solution dropwise to pre-dried and dehydrated activated carbon carrier powder using a normal pressure dropping funnel, and stir thoroughly to impregnate the powder by equal volume until fully loaded. The activated carbon carrier has an average surface area of ​​800 m². 2 / g, with an average particle size of 0.2 mm.

[0072] 2) The impregnated powder was transferred to a vacuum drying oven for processing. After being evacuated, it was heated to 200 °C and dried for 24 hours. The calcined powder was then transferred to a tube furnace and calcined at 400 °C for 4 hours under inert gas protection, and then cooled to room temperature.

[0073] 3) Then, the temperature is programmed to rise to 150 °C at a rate of 2 °C / min, and reduced with a 1% H2 / 99% Ar mixed gas for 2 h; then the temperature is programmed to rise to 400 °C at a rate of 2 °C / min, and then pure H2 is used for 3 h; finally, the temperature is programmed to rise to 600 °C at a rate of 5 °C / min and maintained for 1 h, and then cooled and passivated for later use.

[0074] 200 mg of catalyst was transferred to a high-pressure reactor. Synthesis gas with 25% ethylene and a 1:1 volume ratio of 75% CO and H2 was introduced to a mixed reaction gas pressure of 4 MPa. The reaction temperature was set to 200 °C. After 15 h of reaction, the types and contents of various components in the product were analyzed by Agilent 8860B chromatography, and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0075] Example 3

[0076] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, the method comprising the following steps:

[0077] 1) A 0.01 g / mL RbNO3 solution and a 0.05 g / mL Ni(NO3)2 solution were mixed at a mass ratio of Rb:Ni = 1:5. Under constant temperature water bath conditions of 60 °C, the precursor solution was slowly added dropwise to pre-dried and dehydrated activated carbon carrier powder using a normal pressure dropping funnel, and the mixture was thoroughly stirred to achieve equal volume impregnation until fully loaded. The activated carbon carrier had an average surface area of ​​800 m². 2 / g, with an average particle size of 0.2 mm.

[0078] 2) The impregnated powder was transferred to a vacuum drying oven for processing. After being evacuated, it was heated to 200 °C and dried for 24 hours. The calcined powder was then transferred to a tube furnace and calcined at 400 °C for 4 hours under inert gas protection, and then cooled to room temperature.

[0079] 3) Then, the temperature is programmed to 150 ℃ at a rate of 2 ℃ / min, and reduced with a 1% H2 / 99% Ar mixed gas for 2 h; then the temperature is programmed to 400 ℃ at a rate of 2 ℃ / min, and then pure H2 is used for 3 h; finally, the temperature is programmed to 600 ℃ at a rate of 5 ℃ / min and maintained for 1 h, and then cooled and passivated for later use.

[0080] 200 mg of catalyst was transferred to a high-pressure reactor. Synthesis gas with 25% ethylene and a 1:1 volume ratio of 75% CO and H2 was introduced to a mixed reaction gas pressure of 4 MPa. The reaction temperature was set to 200 °C. After 15 h of reaction, the types and contents of various components in the product were analyzed by Agilent 8860B chromatography, and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0081] Example 4

[0082] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, the method comprising the following steps:

[0083] 1) A 0.01 g / mL CsNO3 solution and a 0.05 g / mL Ni(NO3)2 solution were mixed at a Cs:Ni ratio of 1:5. Under constant temperature water bath conditions of 60 °C, the precursor solution was slowly added dropwise to pre-dried and dehydrated activated carbon carrier powder using a normal pressure dropping funnel, and the mixture was stirred thoroughly to achieve equal volume impregnation until fully loaded. The activated carbon carrier had an average surface area of ​​800 m². 2 / g, with an average particle size of 0.2 mm.

[0084] 2) The impregnated powder was transferred to a vacuum drying oven for processing. After being evacuated, it was heated to 200 °C and dried for 24 hours. The calcined powder was then transferred to a tube furnace and calcined at 400 °C for 4 hours under inert gas protection, and then cooled to room temperature.

[0085] 3) Then, the temperature is programmed to 150 ℃ at a rate of 2 ℃ / min, and reduced with a 1% H2 / 99% Ar mixed gas for 2 h; then the temperature is programmed to 400 ℃ at a rate of 2 ℃ / min, and then pure H2 is used for 3 h; finally, the temperature is programmed to 600 ℃ at a rate of 5 ℃ / min and maintained for 1 h, and then cooled and passivated for later use.

[0086] 200 mg of catalyst was transferred to a high-pressure reactor. Synthesis gas with 25% ethylene and a 1:1 volume ratio of 75% CO and H2 was introduced to a mixed reaction gas pressure of 4 MPa. The reaction temperature was set to 200 °C. After 15 h of reaction, the types and contents of various components in the product were analyzed by Agilent 8860B chromatography, and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0087] Example 5

[0088] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, and the preparation method is the same as that in Example 1.

[0089] The catalytic reaction conditions differ from those in Example 1 in that the proportion of ethylene is 50%. The catalytic results are tested using the same method as in Example 1, and the reaction results are shown in Table 1.

[0090] Example 6

[0091] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, and the preparation method is the same as that in Example 1.

[0092] The reaction conditions described in this catalysis differ from those in Example 1 in that the reaction pressure is 2 MPa. The test method for the catalytic results is the same as that in Example 1, and the reaction results are shown in Table 1.

[0093] Example 7

[0094] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, the method comprising the following steps:

[0095] 1) Mix 0.01 g / mL Mg(NO3)2 solution and 0.05 g / mL Ni(NO3)2 solution at a mass ratio of Mg:Ni = 1:5. Under constant temperature water bath conditions of 60 ℃, slowly add the precursor solution dropwise to pre-dried and dehydrated activated carbon carrier powder using a normal pressure dropping funnel, and stir thoroughly to impregnate the powder by equal volume until fully loaded. The activated carbon carrier has an average surface area of ​​800 m². 2 / g, with an average particle size of 0.2 mm.

[0096] 2) The impregnated powder was transferred to a vacuum drying oven for processing. After being evacuated, it was heated to 200 °C and dried for 24 hours. The calcined powder was then transferred to a tube furnace and calcined at 400 °C for 4 hours under inert gas protection, and then cooled to room temperature.

[0097] 3) Then, the temperature is programmed to 150 ℃ at a rate of 2 ℃ / min, and reduced with a 1% H2 / 99% Ar mixed gas for 2 h; then the temperature is programmed to 400 ℃ at a rate of 2 ℃ / min, and then pure H2 is used for 3 h; finally, the temperature is programmed to 600 ℃ at a rate of 5 ℃ / min and maintained for 1 h, and then cooled and passivated for later use.

[0098] 200 mg of catalyst was transferred to a high-pressure reactor. Synthesis gas with 25% ethylene and a 1:1 volume ratio of 75% CO and H2 was introduced to a mixed reaction gas pressure of 4 MPa. The reaction temperature was set to 200 °C. After 15 h of reaction, the types and contents of various components in the product were analyzed by Agilent 8860B chromatography, and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0099] Example 8

[0100] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, the method comprising the following steps:

[0101] 1) Mix 0.01 g / mL Ba(NO3)2 solution and 0.05 g / mL Ni(NO3)2 solution at a mass ratio of Ba:Ni = 1:5. Under constant temperature water bath conditions of 60 ℃, slowly add the precursor solution dropwise to pre-dried and dehydrated activated carbon carrier powder using a normal pressure dropping funnel, and stir thoroughly to impregnate the powder by equal volume until fully loaded. The activated carbon carrier has an average surface area of ​​800 m². 2 / g, with an average particle size of 0.2 mm.

[0102] 2) The impregnated powder was transferred to a vacuum drying oven for processing. After being evacuated, it was heated to 200 °C and dried for 24 hours. The calcined powder was then transferred to a tube furnace and calcined at 400 °C for 4 hours under inert gas protection, and then cooled to room temperature.

[0103] 3) Then, the temperature is programmed to 150 ℃ at a rate of 2 ℃ / min, and reduced with a 1% H2 / 99% Ar mixed gas for 2 h; then the temperature is programmed to 400 ℃ at a rate of 2 ℃ / min, and then pure H2 is used for 3 h; finally, the temperature is programmed to 600 ℃ at a rate of 5 ℃ / min and maintained for 1 h, and then cooled and passivated for later use.

[0104] 200 mg of catalyst was transferred to a high-pressure reactor. Synthesis gas with 25% ethylene and a 1:1 volume ratio of 75% CO and H2 was introduced to a mixed reaction gas pressure of 4 MPa. The reaction temperature was set to 200 °C. After 15 h of reaction, the types and contents of various components in the product were analyzed by Agilent 8860B chromatography, and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0105] Example 9

[0106] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, the method comprising the following steps:

[0107] 1) Mix 0.01 g / mL NaNO3 solution and 0.02 g / mL Ni(NO3)2 solution at a Na:Ni mass ratio of 1:2. Under constant temperature water bath conditions of 60 ℃, slowly add the precursor solution dropwise to pre-dried and dehydrated activated carbon carrier powder using a normal pressure dropping funnel, and stir thoroughly to impregnate the powder by equal volume until fully loaded. The activated carbon carrier has an average surface area of ​​800 m². 2 / g, with an average particle size of 0.2 mm.

[0108] 2) The impregnated powder was transferred to a vacuum drying oven for processing. After being evacuated, it was heated to 200 °C and dried for 24 hours. The calcined powder was then transferred to a tube furnace and calcined at 400 °C for 4 hours under inert gas protection, and then cooled to room temperature.

[0109] 3) Then, the temperature is programmed to 150 ℃ at a rate of 2 ℃ / min, and reduced with a 1% H2 / 99% Ar mixed gas for 2 h; then the temperature is programmed to 400 ℃ at a rate of 2 ℃ / min, and then pure H2 is used for 3 h; finally, the temperature is programmed to 600 ℃ at a rate of 5 ℃ / min and maintained for 1 h, and then cooled and passivated for later use.

[0110] 200 mg of catalyst was transferred to a high-pressure reactor. Synthesis gas with 25% ethylene and a 1:1 volume ratio of 75% CO and H2 was introduced to a mixed reaction gas pressure of 4 MPa. The reaction temperature was set to 200 °C. After 15 h of reaction, the types and contents of various components in the product were analyzed by Agilent 8860B chromatography, and the conversion rate and selectivity of the reaction were calculated accordingly. The reaction results are shown in Table 1.

[0111] Example 10

[0112] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, the method comprising the following steps:

[0113] 1) Mix 0.01 g / mL NaNO3 solution and 0.2 g / mL Ni(NO3)2 solution at a mass ratio of Na:Ni = 1:20. Under constant temperature water bath conditions of 60 ℃, slowly add the precursor solution dropwise to pre-dried and dehydrated activated carbon carrier powder using a normal pressure dropping funnel, and stir thoroughly to impregnate the powder in equal volumes until fully loaded. The activated carbon carrier has an average surface area of ​​800 m². 2 / g, with an average particle size of 0.2 mm.

[0114] 2) The impregnated powder was transferred to a vacuum drying oven for processing. After being evacuated, it was heated to 200 °C and dried for 24 hours. The calcined powder was then transferred to a tube furnace and calcined at 400 °C for 4 hours under inert gas protection, and then cooled to room temperature.

[0115] 3) Then, the temperature is programmed to 150 ℃ at a rate of 2 ℃ / min, and reduced with a 1% H2 / 99% Ar mixed gas for 2 h; then the temperature is programmed to 400 ℃ at a rate of 2 ℃ / min, and then pure H2 is used for 3 h; finally, the temperature is programmed to 600 ℃ at a rate of 5 ℃ / min and maintained for 1 h, and then cooled and passivated for later use.

[0116] 200 mg of catalyst was transferred to a high-pressure reactor. Syngas, consisting of 25% ethylene and 75% CO and H2 in a 1:1 volume ratio, was introduced to a mixed reaction pressure of 4 MPa. The reaction temperature was set to 200 °C. After 15 h of reaction, the types and contents of various components in the product were analyzed using an Agilent 8860B chromatograph. The conversion rate and selectivity of the reaction were calculated accordingly. The results are shown in Table 1.

[0117] Comparative Example 1

[0118] This comparative example provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins. The difference between this preparation method and Example 1 is that in step 1), the precursor solution is injected into the activated carbon support powder in excess under a constant temperature water bath at 60 °C, and then transferred to a rotary evaporator for vacuum distillation until the solution is completely evaporated.

[0119] The reaction conditions and test methods for the catalyst were the same as in Example 1, and the reaction results are shown in Table 1.

[0120] Comparative Example 2

[0121] This comparative example provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins. The difference between this preparation method and Example 1 is that in step 2), the impregnated powder is transferred to a tube furnace for processing and heated to 200 °C for drying under Ar protection for 24 h.

[0122] The reaction conditions and test methods for the catalyst were the same as in Example 1, and the reaction results are shown in Table 1.

[0123] Comparative Example 3

[0124] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, and the preparation method is the same as that in Example 1.

[0125] The reaction conditions described in this catalysis differ from those in Example 1 in that the reaction temperature is 100°C. The test method for the catalytic results is the same as that in Example 1, and the reaction results are shown in Table 1.

[0126] Comparative Example 4

[0127] This embodiment provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins, and the preparation method is the same as that in Example 1.

[0128] The catalytic reaction conditions differ from those in Example 1 in that the reaction time is 5 h, and the catalytic result testing method is the same as that in Example 1. The reaction results are shown in Table 1.

[0129] Comparative Example 5

[0130] This comparative example provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins. The difference between this preparation method and Example 1 is that in step 1), 0.01 g / mL NaNO3 solution and 0.01 g / mL Ni(NO3)2 solution are mixed at a mass ratio of Na:Ni = 1:1.

[0131] The reaction conditions and test methods for the catalyst were the same as in Example 1, and the reaction results are shown in Table 1.

[0132] Comparative Example 6

[0133] This comparative example provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins. The difference between this preparation method and Example 1 is that in step 1), 0.01 g / mL NaNO3 solution and 0.3 g / mL Ni(NO3)2 solution are mixed at a mass ratio of Na:Ni = 1:30.

[0134] The reaction conditions and test methods for the catalyst were the same as in Example 1, and the reaction results are shown in Table 1.

[0135] Comparative Example 7

[0136] This comparative example provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins. The difference between this preparation method and Example 1 is that no additional alkali metal promoter is added in step 1).

[0137] The reaction conditions and test methods for the catalyst were the same as in Example 1, and the reaction results are shown in Table 1.

[0138] Comparative Example 8

[0139] This comparative example provides a method for preparing a nickel-based catalyst for the hydroformylation reaction of olefins. The difference between this preparation method and Example 1 is that in step 1), the support is changed to SiO2-380 aerosol.

[0140] The reaction conditions and test methods for the catalyst were the same as in Example 1, and the reaction results are shown in Table 1.

[0141] Table 1. Catalyst reaction results of Examples 1-11 and Comparative Examples 1-8

[0142]

[0143] Under the same reaction conditions and catalyst composition, Comparative Example 1, due to the excessive impregnation of the precursor solution into the activated carbon support powder in one go, resulted in uneven distribution of the active components in the support, leading to a significant decrease in the selectivity of propanol and propionaldehyde compared to Example 1, which had the same composition but was impregnated slowly in equal volumes.

[0144] Under the same reaction conditions and catalyst composition, Comparative Example 2, due to drying under Ar protection, caused water vapor to erupt from the support during the drying process, affecting the distribution and content of the active components, resulting in a significant decrease in the selectivity of propanol and propionaldehyde compared to Example 1, which had the same composition but was vacuum dried.

[0145] With the same catalyst composition and preparation method, Comparative Examples 3 and 4 showed a significant decrease in the selectivity of propanol and propanal compared to Example 1 with the same composition due to insufficient reaction temperature or time.

[0146] Under the same reaction conditions and preparation methods, Comparative Example 5 suffered from a significant decrease in ethylene conversion rate due to the excessively low Ni content in the catalyst, as seen in Example 1. The ethylene conversion rate was less than 1.5%, which may lead to inaccurate results for subsequent product selectivity.

[0147] Under the same reaction conditions and preparation methods, Comparative Example 6 had a much higher selectivity for the byproduct ethane than Example 1 due to the excessively high Ni content in the catalyst.

[0148] Under the same reaction conditions and preparation methods, Comparative Example 7 produced almost only ethane in the reaction because the catalyst did not contain any auxiliary agents.

[0149] Under the same reaction conditions, Comparative Example 8, due to the selection of SiO2-380 aerosol as the catalyst support, resulted in a much higher selectivity for the byproduct ethane compared to Example 1, with other components and preparation methods remaining the same.

[0150] In Examples 1-10 of this application, the overall catalyst activity and selectivity for propanal and propanol vary depending on the type and content of the additives. When the additive is Na, the overall catalyst activity and selectivity for propanal and propanol are optimal. In actual production, the additives and component ratios can be selected as needed.

[0151] The results above show that the catalyst described in this application, under the same reaction conditions, exhibits high activity, high selectivity for propanol and propanal, and low selectivity for byproducts. Specifically, in the catalyst described in the embodiments of this application, when catalyzing the hydroformylation of ethylene to prepare propanal and propanol, a mixed reaction gas was introduced at a pressure of 4 MPa with an ethylene ratio of 25%, and the reaction temperature was set to 200 °C. After 15 h of reaction, the combined selectivity of propanal and propanol reached as high as 70%, far exceeding that of the comparative example, while the selectivity for the byproduct ethane was relatively low.

[0152] This invention effectively overcomes the various shortcomings of the prior art and has high industrial application value.

[0153] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A nickel-based catalyst for the hydroformylation of olefins, characterized in that, The catalyst comprises an active component and a C support. The active component comprises Ni and an auxiliary agent. The active component is supported on the C support. The auxiliary agent is selected from alkali metals and / or alkaline earth metals. Based on the total mass of the catalyst, the content of Ni is 0.2~20 wt%, and the content of the auxiliary agent is 0.1~5 wt%.

2. The catalyst according to claim 1, characterized in that, The additive is selected from one or more of Li, Na, K, Rb, Cs, Mg, and Ba.

3. The catalyst according to claim 1, characterized in that, The C carrier is selected from one or more of activated carbon, coconut shell carbon, carbon nitride, and graphite powder; And / or, the specific surface area of ​​the C-carrier is 600–1200 m². 2 / g; And / or, the particle size of the C-carrier is 0.1~0.4 mm.

4. A method for preparing a catalyst according to any one of claims 1 to 3, characterized in that, The preparation method includes the following steps: impregnating the C support with a mixed aqueous solution of Ni and the soluble salt corresponding to the additive, and then drying and calcining.

5. The preparation method according to claim 1, characterized in that, The impregnation is an equal-volume impregnation; And / or, the immersion is carried out in a constant temperature water bath; And / or, the soluble salt of Ni corresponding to the auxiliary agent is selected from one or more of nitrates, chlorides, and sulfates; And / or, in the mixed aqueous solution, the molar ratio of Ni to the additive is 1:2~20; And / or, the concentration of Ni and the soluble salt corresponding to the additive in the mixed aqueous solution is 0.2~2 g / mL; And / or, the drying is carried out in a vacuum environment; And / or, the drying temperature is 50~200℃; And / or, the drying time is 5~20 h; And / or, the calcination temperature is 200~400 ℃; And / or, the roasting time is 4 to 6 hours.

6. Use of a catalyst as described in any one of claims 1 to 3 in the catalytic hydroformylation of olefins.

7. A method for catalyzing the hydroformylation reaction of olefins using the catalyst as described in any one of claims 1 to 3.

8. The method according to claim 7, characterized in that, The reaction also includes a step of reducing the catalyst. And / or, the reaction gas of the reaction includes ethylene, CO and H2, with a volume ratio of ethylene:CO:H2 of 1:(0.5~2):(0.5~2); And / or, the pressure of the reaction is 2~4 MPa; And / or, the reaction temperature is 180~200 °C. And / or, the reaction time is 15-20 h.

9. The method according to claim 8, characterized in that, The atmosphere for the reduction treatment is selected from one or more of the following: a mixture of argon and hydrogen, or pure hydrogen. And / or, the reduction process takes 3 to 10 hours; And / or, the reduction treatment temperature is 120~650℃; And / or, the pressure of the reduction treatment is 0~2MPa; And / or, the space velocity of the reduction process is 6000~8000 h⁻¹. -1 ; And / or, the proportion of ethylene in the reaction gas is 20% to 50%.

10. The method according to claim 9, characterized in that, The ratio of H2 to Ar in the atmosphere is 1:9~99; And / or, the reduction process includes three heating programs: the first heating program has a temperature of 150℃-180℃ and a reduction time of 1-3 h, with a reduction atmosphere of a mixture of H2 and Ar; the second heating program has a temperature of 370℃-410℃ and a reduction time of 1-5 h, with a reduction atmosphere of H2; and the third heating program has a temperature of 580℃-600℃ and a reduction time of 1-3 h, with a reduction atmosphere of H2.

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