A catalyst for the production of oxygenates by the hydroformylation of olefins and a process for its preparation and use

Abstract

The present application provides a catalyst for preparing oxygen-containing compounds by olefin hydroformylation reaction, and a preparation method and use thereof, the catalyst is Fe x Co y M, the catalyst contains 0.1-15wt% M, 85-99.9wt% Fe and Co, the atomic ratio of x to y is 0.1-10, and M is a metal element. When the catalyst is used for preparing oxygen-containing compounds by olefin hydroformylation reaction, the conversion rate of olefin can reach 93-99.9%, and the selectivity of oxygen-containing compounds can reach 89-98.8%; and the catalyst is in a solid state during the reaction, which is easy to realize solid-liquid separation with the product, and also avoids the loss of the catalyst during the separation process.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation technology, and in particular to a catalyst for the preparation of oxygen-containing compounds by olefin hydroformylation reaction, its preparation method, and its uses. Background Technology

[0002] Hydroformylation is a reaction in which olefins are converted into aldehydes or alcohols under a feed gas atmosphere of CO and H2. It is an important pathway for the high-value conversion and utilization of olefins. Globally, more than 10 million tons of olefins are converted to high-value products through this reaction pathway every year.

[0003] Various transition metal carbonyl complexes catalyze the hydroformylation of olefins, but only cobalt and rhodium carbonyl complexes are suitable for industrial production. The catalytically active component of the cobalt catalyst is tetracobalt hydroxya, generated from cobalt octacarbonyldicobalt. Cobalt octacarbonyldicobalt is prepared by reacting metallic cobalt, cobalt oxide, cobalt carbonate, or cobalt fatty acid salts with the feed gas CO and H2. Because cobalt octacarbonyldicobalt decomposes readily even at room temperature, the cobalt catalyst preparation process must be carried out under high CO partial pressures to obtain more tetracobalt hydroxya. Furthermore, the use of cobalt catalysts also presents challenges such as difficult catalyst recovery, limited reusability, and equipment corrosion. Rhodium catalysts exhibit high activity and good thermal stability, and their preparation process is less demanding in terms of pressure. However, because the rhodium catalyst, feedstock, and product are in the same phase, rhodium loss is inevitable during catalyst separation and recovery after the reaction. This problem is particularly pronounced due to the significant increase in rhodium prices in recent years. Summary of the Invention

[0004] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a catalyst for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, a method for preparing the catalyst and its uses, so as to obtain a catalyst that has both the high activity and high selectivity of a homogeneous catalyst and the advantages of a supported solid catalyst, namely, easy separation of the product and the catalyst.

[0005] To achieve the above and other related objectives, the present invention is obtained through the following technical solution.

[0006] This invention provides a catalyst for the hydroformylation reaction of olefins to prepare oxygen-containing compounds, wherein the catalyst is Fe. x Co y M, the catalyst contains 0.1–15 wt% M and 85–99.9 wt% Fe and Co, the atomic ratio of x to y is 0.1–10, and M is a metallic element. The ratio of x to y represents the molar ratio of Fe and Co in the catalyst.

[0007] For example, the ratio of the number of atoms of x to y can be 0.1~0.3, 0.3~0.5, 0.5~1.0, 1.0~2.0, 2.0~3.0, 3.0~6.0, 6.0~8.0, or 8.0~10.

[0008] The content of element M in the catalyst is 0.1–0.2 wt%, 0.2–0.3 wt%, 0.3–0.4 wt%, 0.4–0.5 wt%, 0.5–0.6 wt%, 0.6–0.7 wt%, 0.7–0.8 wt%, 0.8–0.9 wt%, 0.9–1.0 wt%, 1.0–5 wt%, 5–10 wt%, and 10–15 wt%.

[0009] The Fe and Co contents in the catalyst are 85–90 wt%, 90–92 wt%, 90–95 wt%, 95–97 wt%, 97–98.9 wt%, and 98.9–99.9 wt%, respectively.

[0010] Preferably, M is one or more selected from Li, Na, K, Rb, and Cs.

[0011] Preferably, the catalyst includes carbon (C) and contains 0.1–10 wt% M, 1–10 wt% C, 85–98.9 wt% Fe, and Co.

[0012] The C content in the catalyst is 1-2 wt%, 2-3 wt%, 3-5 wt%, 5-7 wt%, 7-9 wt%, or 9-10 wt%.

[0013] The present invention also provides a method for preparing the catalyst as described above, using soluble salts corresponding to Fe and Co and a precipitant containing M as raw materials, and preparing it by co-precipitation method.

[0014] Preferably, the coprecipitation method is as follows: a solution of the soluble salts corresponding to Fe and Co is brought into contact with a precipitant solution to trigger a coprecipitation reaction, resulting in a precipitate, which is then calcined.

[0015] More preferably, aging, centrifugation, washing and drying are performed before roasting.

[0016] More preferably, the aging temperature is 20–80°C, more preferably 50–55°C.

[0017] More preferably, the aging time is 0.5 to 10 hours, more preferably 2 to 3 hours.

[0018] More preferably, the number of centrifugation and washing cycles is 1 to 10, more preferably 5 to 6.

[0019] More preferably, the drying temperature is 50–120°C, more preferably 110–120°C.

[0020] More preferably, the drying time is 5 to 24 hours, more preferably 20 to 24 hours.

[0021] More preferably, the roasting temperature is 300–600℃, more preferably 350–400℃.

[0022] More preferably, the roasting time is 2 to 10 hours, more preferably 4 to 6 hours.

[0023] More preferably, in the solution of the soluble salts corresponding to Fe and Co, the sum of the molar concentrations of Fe and Co elements is 0.1–2.0 mol / L. More preferably, it is 1.0–2.0 mol / L.

[0024] More preferably, the molar concentration of element M in the precipitant solution is 0.1 to 2.0 mol / L, preferably 1.0 to 2.0 mol / L.

[0025] Preferably, the coprecipitation reaction temperature is 10–80°C, such as 10–40°C, 40–50°C, 50–60°C, 60–70°C, or 70–80°C.

[0026] Preferably, the pH of the coprecipitation reaction system is 7 to 12, more preferably 8.0 to 8.5.

[0027] Preferably, the soluble salt corresponding to Fe is one or more selected from ferric chloride, ferric nitrate, ferric sulfate, and ferric acetate.

[0028] Preferably, the soluble salt corresponding to Co is one or more selected from cobalt chloride, cobalt nitrate, cobalt sulfate, and cobalt acetate.

[0029] Preferably, the precipitant containing M is selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, LiOH, NaOH, KOH, RbOH and CsOH.

[0030] Preferably, the catalyst is subjected to reduction and carbonization treatment.

[0031] More preferably, the reduction temperature is 300–500°C. For example, it can be 300–400°C or 400–500°C.

[0032] More preferably, the reduction pressure is 0.1 to 1.0 MPa, such as 0.1 to 0.5 MPa or 0.5 to 1.0 MPa.

[0033] More preferably, the reduction time is 5 to 10 hours. For example, it can be 5 to 6 hours, 6 to 7 hours, 7 to 8 hours, 8 to 9 hours, or 9 to 10 hours.

[0034] More preferably, the reduction space velocity is 1000–20000 h⁻¹ -1 .

[0035] More preferably, the reducing atmosphere is hydrogen. Even more preferably, the reducing atmosphere is a mixture of hydrogen and an inert gas, wherein the volume percentage of hydrogen in the mixture is 5-50%.

[0036] More preferably, the carbonization atmosphere is CO, and even more preferably, it is a mixture of H2 and CO, with an H2 / CO (molar ratio) of 0.5 to 2.0.

[0037] More preferably, the carbonization space velocity is 500–2000 h⁻¹. -1 .

[0038] More preferably, the carbonization pressure is 0.1 to 1.0 MPa, such as 0.1 to 0.5 MPa, 0.5 to 0.8 MPa, or 0.8 to 1.0 MPa.

[0039] More preferably, the carbonization time is 5 to 24 hours. For example, it can be 5 to 10 hours, 10 to 15 hours, 15 to 20 hours, or 20 to 24 hours, and more preferably 10 to 15 hours.

[0040] More preferably, the carbonization temperature is 200–300°C, such as 200–250°C, 250–300°C, and more preferably 250–300°C.

[0041] This invention also provides the application of the catalyst described above in the preparation of oxygen-containing compounds by the hydroformylation of olefins.

[0042] Preferably, the oxygen-containing compound includes alcohols, aldehydes, and acids.

[0043] Preferably, the hydroformylation reaction temperature is 100–200°C. For example, it can be 100–150°C, 150–180°C, or 180–200°C.

[0044] Preferably, the reaction time for the hydroformylation reaction is 1–20 h. For example, it can be 1–10 h or 10–20 h.

[0045] Preferably, the reaction pressure of the hydroformylation reaction is 1.0–6.0 MPa. For example, it can be 1.0–2.0 MPa, 2.0–3.0 MPa, 3.0–4.0 MPa, 4.0–5.0 MPa, or 5.0–6.0 MPa.

[0046] Preferably, the stirring speed is 500–2000 rpm. For example, it can be 500–1000 rpm, 1000–1500 rpm, or 1500–2000 rpm.

[0047] Preferably, the hydroformylation reaction system includes a feed gas, which is a mixture of H2 and CO with a molar ratio of 0.5 to 2.0. For example, it can be 0.5 to 1.0 or 1.2 to 2.0.

[0048] Preferably, the hydroformylation reaction system includes a solvent, which is one or more selected from cyclohexane, decane, undecane, and dodecane.

[0049] More preferably, the volume ratio of the olefin to the solvent is 1:(9-20), even more preferably 1:(9-15).

[0050] Preferably, the olefin is an α-olefin. More preferably, the α-olefin is an α-olefin with 5 to 18 carbon atoms, such as 1-octene and 1-decene.

[0051] Preferably, the mass-to-volume ratio of the catalyst to the olefin is 10–200 mg / mL. For example, it can be 10–100 mg / mL, 100–160 mg / mL, or 160–200 mg / mL.

[0052] The catalyst Fe disclosed in this invention x Co y M is an alloy catalyst that is pretreated before the hydroformylation reaction of olefins. Carbon is introduced through carbonization to form a unique Fe / Co dual-active metal carbide interface as an active site.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] 1. The catalyst, in the hydroformylation reaction of olefins to prepare oxygen-containing compounds, can achieve an olefin conversion rate of up to [percentage missing].

[0055] The selectivity for oxygen-containing compounds can reach 89-98.8%, with a range of 93-99.9%.

[0056] 2. The catalyst is solid during the reaction, which makes it easy to separate from the product into solid and liquid phases, and also avoids the loss of catalyst during the separation process;

[0057] 3. It is not corrosive to equipment and still exhibits good catalytic effect after 200 hours of use. The catalyst has good recycling performance.

[0058] 4. The preparation method is simple and suitable for large-scale industrial production. Attached Figure Description

[0059] Figure 1 The image shown is the XRD pattern of the catalyst prepared in Example 6 of this invention.

[0060] Figure 2The image shown is the XRD pattern of the catalyst prepared in Comparative Example 1 of this invention. Detailed Implementation

[0061] 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.

[0062] 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.

[0063] 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.

[0064] This embodiment provides a specific catalyst for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, wherein the catalyst is Fe x Co y In CM, the atomic ratio of x to y is 0.1 to 10, and the catalyst contains 0.1 to 10 wt% M, 10 wt% C, and 85 to 98.9 wt% Fe and Co. M is selected from one or more of Li, Na, K, Rb, and Cs.

[0065] The catalyst is prepared as follows:

[0066] (1) The co-precipitation reaction is triggered by simultaneously adding the solutions of Fe and Co soluble salts and the precipitant solution to water to obtain the precipitate. After aging, centrifugation, washing, drying and calcination, the precursor is obtained.

[0067] In the solution, the molar concentration of the soluble salts corresponding to Fe and Co is 0.1–0.2 mol / L. In the precipitant solution, the molar concentration of M is 0.1–2.0 mol / L.

[0068] The coprecipitation reaction temperature is 10–80℃, and the pH of the coprecipitation reaction system is 6–12.

[0069] (2) The precursor is reduced and carbonized to obtain the catalyst.

[0070] The reducing atmosphere is hydrogen, and the reducing space velocity is 1000–20000 h⁻¹. -1 The reduction pressure is 0.1–1.0 MPa, the reduction temperature is 300–500℃, and the reduction time is 5–10 h. After reduction, the temperature is lowered to the carbonization temperature (200–300℃), and the carbonization atmosphere is switched to begin the carbonization process, maintaining a carbonization space velocity of 500–2000 h⁻¹. -1 The carbonization pressure is 0.1–1.0 MPa, and the carbonization time is 5–24 h. The catalyst is obtained after the carbonization process is completed.

[0071] (3) The catalyst is used in the hydroformylation reaction of olefins to prepare oxygen-containing compounds.

[0072] The catalyst is compressed into tablets, sieved, and then loaded into a batch small reactor. The particle size of the catalyst is 40-60 mesh. Olefins and solvents are added in a volume ratio of 1:(9-20), and the mass-volume ratio of catalyst to olefins is 1.0-20 mg / mL. A mixture of H2 / CO molar ratio of 0.5-2.0 is introduced as the feed gas. After the back pressure is increased to 1.0-6.0 MPa, the temperature is raised to 100-200℃ to carry out the hydroformylation reaction to prepare oxygen-containing compounds. The stirring speed is 500-2000 rpm, and the reaction time is 1-20 h.

[0073] The following provides more specific examples for illustration.

[0074] Example 1

[0075] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an atomic ratio of x to y of 1:1, a Co element mass of 50 wt% of the catalyst mass, a Na element mass of 1.0 wt% of the catalyst mass, and a Fe element mass of 47% of the catalyst mass, denoted as 47Fe-50Co-C-1Na.

[0076] This embodiment also provides a method for preparing the catalyst described above, the specific steps of which are as follows:

[0077] (1) Weigh cobalt nitrate and ferric nitrate according to the principle that Co accounts for 50% of the total mass of the catalyst and the Fe / Co molar ratio is 1:1, and dissolve them in water to form a salt solution. The total molar concentration of cobalt and iron in the salt solution is 1.0 mol / L. Weigh Na2CO3 according to the principle that Na accounts for 1.0% of the total mass of the catalyst and dissolve it in water to prepare a Na2CO3 solution. The molar concentration of Na in the Na2CO3 solution is 1.0 mol / L.

[0078] The salt solution and Na2CO3 solution were simultaneously added dropwise to water to trigger a coprecipitation reaction at a reaction temperature of 50°C.

[0079] The pH was 8.0. After filtration, the precipitate was obtained and then aged, centrifuged, washed, dried and calcined to obtain the precursor.

[0080] The aging temperature was 50℃, the aging time was 2h, the number of centrifugation and washing cycles were 5, the drying temperature was 120℃, the drying time was 24h, the calcination temperature was 400℃, and the calcination time was 4h.

[0081] (2) The precursor is reduced and carbonized to obtain the catalyst.

[0082] The reducing atmosphere used was pure H2, and the reduction was carried out at 400℃ and 0.5MPa for 5 hours, with a reduction space velocity of 10000 h⁻¹. -1 After reduction, the temperature is lowered to 250℃, and the carbonization atmosphere is switched to begin the carbonization process. The carbonization atmosphere is pure CO, and the carbonization space velocity is maintained at 2000 h⁻¹. -1 The carbonization pressure was 0.5 MPa, and the carbonization time was 10 hours. The catalyst was obtained after the carbonization process was completed.

[0083] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, and the specific steps are as follows:

[0084] The catalyst was pressed into tablets and sieved. 100 mg of 40-60 mesh catalyst was weighed and loaded into a batch reactor. 1-Octene and cyclohexane were added, with a total volume of 10 mL. The volume ratio of 1-octene to cyclohexane was 1:9, and the mass-to-volume ratio of catalyst to 1-octene was 100 mg / mL. A mixture of H₂ / CO with a molar ratio of 1 was introduced as the feed gas. After the back pressure was increased to 4 MPa, the temperature was raised to 150 °C, and the magnetic stirrer was rotated at 1000 rpm to carry out the hydroformylation reaction to prepare oxygen-containing compounds. The reaction time was 10 h. The catalytic results are shown in Table 1.

[0085] Example 2

[0086] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an x ​​to y atomic ratio of 1:1, a Co element mass of 47 wt% of the catalyst mass, a Na element mass of 1.0 wt% of the catalyst mass, and a Fe element mass of 45% of the catalyst mass, denoted as 45Fe-47Co-C-1Na.

[0087] This embodiment also provides a method for preparing the catalyst described above. The method differs from that in Example 1 only in that: cobalt chloride and ferric chloride are weighed according to the following formula: Co accounts for 47 wt% of the total catalyst and the Fe / Co molar ratio is 1:1. The cobalt chloride and ferric chloride are then dissolved in water to form a salt solution, in which the total molar concentration of cobalt and ferric chloride is 1.0 mol / L. Na2CO3 is weighed according to the following formula: Na accounts for 1.0 wt% of the total catalyst and is then dissolved in water to prepare a Na2CO3 solution, in which the molar concentration of Na is 1.0 mol / L.

[0088] The carbonization temperature was 250℃, the carbonization atmosphere was pure CO, and the carbonization space velocity was maintained at 2000 h⁻¹. -1 The carbonization pressure was 0.8 MPa, and the carbonization time was 20 h. All other preparation steps were the same as in Example 1.

[0089] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, and the preparation method is the same as in Example 1. The catalytic results are shown in Table 1.

[0090] Example 3

[0091] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an x ​​to y atomic ratio of 3:1, Co accounting for 23 wt% of the catalyst mass, Na accounting for 1.0 wt% of the catalyst mass, and Fe accounting for 74% of the catalyst mass, denoted as 74Fe3-23Co-C-1Na.

[0092] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 1 is that cobalt chloride and ferric chloride are weighed according to the following formula: Co accounts for 23 wt% of the total catalyst and the Fe / Co molar ratio is 3:1. The cobalt chloride and ferric chloride are then dissolved in water to form a salt solution. The total molar concentration of cobalt and ferric chloride in the salt solution is 1.0 mol / L. All other preparation steps are the same as in Example 1.

[0093] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by olefin hydroformylation reaction, and the preparation method is the same as in Example 1.

[0094] Example 4

[0095] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an x ​​to y atomic ratio of 1:2, Co accounting for 66 wt% of the catalyst mass, Na accounting for 1.0 wt% of the catalyst mass, and Fe accounting for 31% of the catalyst mass, denoted as 31Fe-66Co2-C-1Na.

[0096] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 1 is that cobalt chloride and ferric chloride are weighed according to the following formula: Co accounts for 66 wt% of the total catalyst and the Fe / Co molar ratio is 1:2. The cobalt chloride and ferric chloride are then dissolved in water to form a salt solution. The total molar concentration of cobalt and ferric chloride in the salt solution is 1.0 mol / L. All other preparation steps are the same as in Example 1.

[0097] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, and the preparation method is the same as in Example 1. The catalytic results are shown in Table 1.

[0098] Example 5

[0099] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an x ​​to y atomic ratio of 1:2, Co accounting for 66 wt% of the catalyst mass, K accounting for 1.0 wt% of the catalyst mass, and Fe accounting for 31% of the catalyst mass, denoted as 31Fe-66Co2-C-1K.

[0100] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 4 is that K₂CO₃ is weighed and dissolved in water to prepare a K₂CO₃ solution, with K element accounting for 1.0 wt% of the total catalyst content. The molar concentration of K element in the K₂CO₃ solution is 1.0 mol / L. All other preparation steps are the same as in Example 4.

[0101] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, and the preparation method is the same as in Example 4. The catalytic results are shown in Table 1.

[0102] Example 6

[0103] This embodiment provides a more specific catalyst, prepared using the method of Example 1.

[0104] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins. The preparation method differs from that of Example 1 only in that: 1-decene is used instead of 1-octene, the total volume of 1-decene and cyclohexane is 10 mL, the volume ratio of 1-decene to cyclohexane is 1:15, the mass-to-volume ratio of catalyst to 1-decene is 160 mg / mL, and the reaction temperature is 180 °C. All other preparation steps are the same as in Example 1. The catalytic results are shown in Table 1.

[0105] Figure 1The image shows the XRD pattern of the catalyst prepared in Example 6. As can be seen from the XRD pattern, the diffraction characteristic peaks of the catalyst correspond to the Co2C crystal plane and the Fe2C crystal plane, respectively, indicating that the catalyst prepared in Example 8 has an alloy carbide structure and does not include a metal oxide structure.

[0106] This embodiment also provides a lifetime test for the catalyst described above.

[0107] The reaction solution of the above olefin hydroformylation reaction was filtered to obtain the catalyst. The catalyst was added to a batch small reactor and the cycle was repeated for 200 h. The catalytic results are shown in Table 1.

[0108] Example 7

[0109] This embodiment provides a more specific catalyst, prepared using the method of Example 6.

[0110] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins. The only difference between this embodiment and Example 6 is that 1-decene and cyclohexane are added in a total volume of 10 mL, the volume ratio of 1-decene to cyclohexane is 1:9, and the mass-to-volume ratio of catalyst to 1-octene is 100 mg / mL. All other steps are the same as in Example 6. The catalytic results are shown in Table 1.

[0111] Example 8

[0112] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an x ​​to y atomic ratio of 2:1, Co accounting for 33.5 wt% of the catalyst mass, Na accounting for 1.0 wt% of the catalyst mass, and Fe accounting for 63.5% of the catalyst mass, denoted as 63.5Fe2-33.5Co-C-1Na.

[0113] This embodiment also provides a method for preparing the catalyst described above, the specific steps of which are as follows:

[0114] (2) Weigh cobalt chloride and ferric chloride according to the principle that Co accounts for 33.5% of the total catalyst mass and the Fe / Co molar ratio is 2:1, and dissolve them in water to form a salt solution. The total molar concentration of cobalt and iron in the salt solution is 1.0 mol / L. Weigh Na₂CO₃ according to the principle that Na element accounts for 1.0% of the total catalyst mass and dissolve it in water to prepare a Na₂CO₃ solution.

[0115] In the Na2CO3 solution, the molar concentration of Na is 2.0 mol / L.

[0116] The salt solution and Na2CO3 solution were simultaneously added dropwise to water to trigger a coprecipitation reaction at a reaction temperature of 50°C.

[0117] The pH was 8.0. After filtration, the precipitate was obtained and then aged, centrifuged, washed, dried and calcined to obtain the precursor.

[0118] The aging temperature was 50℃, the aging time was 2h, the number of centrifugation and washing cycles were 5, the drying temperature was 120℃, the drying time was 24h, the calcination temperature was 400℃, and the calcination time was 4h.

[0119] (2) The precursor is reduced and carbonized to obtain the catalyst.

[0120] The reducing atmosphere used was pure H2, and the reduction was carried out at 400℃ and 0.5MPa for 5 hours, with a reduction space velocity of 10000 h⁻¹. -1 After reduction, the temperature is lowered to 250℃, and the carbonization atmosphere is switched to begin the carbonization process. The carbonization atmosphere is a mixture of H2 / CO with a molar ratio of 1:1, and the carbonization space velocity is maintained at 2000 h⁻¹. -1 The carbonization pressure was 0.5 MPa, and the carbonization time was 10 hours. The catalyst was obtained after the carbonization process was completed.

[0121] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, and the specific steps are as follows:

[0122] The catalyst was pressed into tablets and sieved. 1 mg of 40-60 mesh catalyst was weighed and loaded into a batch reactor. 1-Octene and cyclohexane were added, with a total volume of 10 mL. The volume ratio of 1-octene to cyclohexane was 1:9, and the mass-to-volume ratio of catalyst to 1-octene was 1 mg / mL. A mixture of H₂ / CO with a molar ratio of 1 was introduced as the feed gas. After the back pressure was increased to 4 MPa, the temperature was raised to 150 °C, and the magnetic stirrer was rotated at 1000 rpm to carry out the hydroformylation reaction to prepare oxygen-containing compounds. The reaction time was 10 h. The catalytic results are shown in Table 1.

[0123] Example 9

[0124] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an x ​​to y atomic ratio of 2:1, Co accounting for 33.5 wt% of the catalyst mass, Na accounting for 1.0 wt% of the catalyst mass, and Fe accounting for 63.5% of the catalyst mass, denoted as 63.5Fe2-33.5Co-C-1Na.

[0125] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 8 is that the carbonization atmosphere is CO; all other preparation steps are the same.

[0126] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, and the preparation method is the same as in Example 8. The catalytic results are shown in Table 1.

[0127] Example 10

[0128] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an x ​​to y atomic ratio of 2:1, Co accounting for 33.5 wt% of the catalyst mass, Na accounting for 1.0 wt% of the catalyst mass, and Fe accounting for 63.5% of the catalyst mass, denoted as 63.5Fe2-33.5Co-C-1Na.

[0129] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 9 is that the carbonization atmosphere is a mixture of H2 / CO with a molar ratio of 2:1; all other preparation steps are the same.

[0130] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, and the preparation method is the same as in Example 9. The catalytic results are shown in Table 1.

[0131] Example 11

[0132] This embodiment provides a more specific catalyst containing a carbide layer, prepared with an x ​​to y atomic ratio of 1:1, a Co element mass of 47 wt% of the catalyst mass, a Na element mass of 0.3 wt% of the catalyst mass, and a Fe element mass of 45% of the catalyst mass, denoted as 45Fe-47Co-C-0.3Na.

[0133] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 1 is that: cobalt nitrate and ferric nitrate are weighed according to the following formula: Co accounts for 47% of the total catalyst mass, and the Fe / Co molar ratio is 1:1. These are then dissolved in water to form a salt solution, in which the total molar concentration of cobalt and iron is 1.0 mol / L. Na₂CO₃ is weighed according to the following formula: Na accounts for 0.3% of the total catalyst mass, and then dissolved in water to prepare a Na₂CO₃ solution, in which the molar concentration of Na is 1.0 mol / L. All other preparation methods are the same.

[0134] This embodiment also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins, and the preparation method is the same as in Example 1. The catalytic results are shown in Table 1.

[0135] Comparative Example 1

[0136] This comparative example is a comparative example of Example 1. This comparative example provides a more specific catalyst containing a carbide layer, prepared according to an atomic ratio of x to y of 1:1, with Co element accounting for 50 wt% of the catalyst mass and Na element accounting for 1.0 wt% of the catalyst mass, wherein the Fe element content is 47%, denoted as 47Fe-50Co-C-1Na.

[0137] The only difference between the preparation method of the catalyst and that of Example 1 is that the reduction temperature is 200℃ and the reduction time is 2h, while the other preparation steps are the same as those of Example 1.

[0138] This comparative example also provides the catalyst described above for the preparation of oxygen-containing compounds by olefin hydroformylation reaction, and the preparation method is the same as that in Example 1.

[0139] Figure 2 The XRD pattern of the catalyst prepared in Comparative Example 1 is shown. As can be seen from the XRD pattern, the diffraction characteristic peaks of the catalyst correspond to the Fe3O4 crystal plane and the Co3O4 crystal plane, respectively, indicating that the catalyst prepared in Comparative Example 1 contains a composite metal oxide phase.

[0140] Comparative Example 2

[0141] This comparative example is a comparative example of Example 1. This comparative example provides a more specific catalyst containing a carbide layer, prepared with an x:y atomic ratio of 1:15, Co accounting for 94 wt% of the catalyst mass, Na accounting for 1.0 wt% of the catalyst mass, and Fe accounting for 6%, denoted as 6Fe-94Co. 10 -C-1Na.

[0142] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 1 is that: cobalt nitrate and ferric nitrate are weighed according to the following formula: Co accounts for 94 wt% of the total catalyst, and the Fe / Co molar ratio is 1:15. The cobalt nitrate and ferric nitrate are then dissolved in water to form a salt solution. The total molar concentration of cobalt and ferric nitrate in the salt solution is 1.0 mol / L. All other preparation steps are the same as in Example 1.

[0143] This comparative example also provides the catalyst described above for the preparation of oxygen-containing compounds by olefin hydroformylation reaction, and the preparation method is the same as that in Example 1.

[0144] Comparative Example 3

[0145] This comparative example is a comparative example of Example 1. This comparative example provides a more specific catalyst containing a carbide layer, prepared with an x:y atomic ratio of 15, Co accounting for 6.6 wt% of the catalyst mass, Na accounting for 1.0 wt% of the catalyst mass, and Fe content of 93.4%, denoted as 93.4Fe. 15 -6.6Co-C-1Na.

[0146] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 1 is that cobalt chloride and ferric chloride are weighed according to the following formula: Co accounts for 6.6 wt% of the total catalyst and the Fe / Co molar ratio is 15. The cobalt chloride and ferric chloride are then dissolved in water to form a salt solution. The total molar concentration of cobalt and ferric chloride in the salt solution is 1.0 mol / L. All other preparation steps are the same as in Example 1.

[0147] This comparative example also provides the catalyst described above for the preparation of oxygen-containing compounds by olefin hydroformylation reaction, and the preparation method is the same as that in Example 1.

[0148] Comparative Example 4

[0149] This comparative example is a comparative example of Example 1. This comparative example provides a more specific catalyst containing a carbide layer, prepared with Fe and Co content of 80wt%, x to y atomic ratio of 1:1, and Na element mass accounting for 1.0wt% of the catalyst mass, wherein Co element content is 41wt% and Fe element content is 39wt%, denoted as 39Fe-41Co-C-1Na.

[0150] This embodiment also provides a method for preparing the catalyst described above. The only difference between this method and Example 1 is that cobalt nitrate and ferric nitrate are weighed according to the following formula: Co accounts for 41 wt% of the total catalyst and the Fe / Co molar ratio is 1:1. The cobalt nitrate and ferric nitrate are then dissolved in water to form a salt solution. The total molar concentration of cobalt and ferric nitrate in the salt solution is 1.0 mol / L. All other preparation steps are the same as in Example 1.

[0151] This comparative example also provides the catalyst described above for the preparation of oxygen-containing compounds by the hydroformylation reaction of olefins. The preparation method is basically the same as that in Example 1, except that the carbonization conditions are different. The carbonization atmosphere is pure CO and the carbonization space velocity is 500 h⁻¹. -1 The carbonization pressure was 2.0 MPa, the carbonization time was 20 h, and the rest of the preparation process was the same as in Example 1.

[0152] Table 1

[0153]

[0154]

[0155] Table 2

[0156]

[0157] As can be seen from Table 2:

[0158] Comparing the data from Examples 1 and 2 and Comparative Example 4, it was found that when the Fe / Co content increased from 92% to 97%, the olefin conversion rate increased from 98.6% to 99.7%, and the selectivity of oxygen-containing compounds increased from 91.0% to 91.7%. This indicates that as the Fe / Co content increases, both the olefin conversion rate and the selectivity of oxygen-containing compounds gradually increase.

[0159] When the Fe / Co content is reduced to 80%, the conversion rate of olefins and the selectivity of oxygen-containing compounds both decrease significantly.

[0160] Based on the data comparison of Examples 1 and 3-4, and Comparative Examples 2-3, it was found that the conversion rate of olefins and the selectivity of oxygen-containing compounds were optimal when the Fe / Co molar ratio was 1:1. When the Fe / Co molar ratio increased or decreased, the conversion rate of olefins and the selectivity of oxygen-containing compounds both decreased. If the Fe / Co molar ratio increased to a very large value, such as 15, or decreased to a very small value, such as 1:15, the conversion rate of olefins and the selectivity of oxygen-containing compounds both decreased significantly.

[0161] A comparison of the data from Examples 1 and 7 revealed that the higher the reaction temperature, the higher the conversion rate of olefins and the higher the selectivity of oxygen-containing compounds.

[0162] A comparison of data from Examples 1 and 6 revealed that increasing the mass-to-volume ratio of catalyst to olefin from 100 mg / mL to 160 mg / mL improved both the conversion rate of olefin and the selectivity of oxygen-containing compounds.

[0163] Comparison of data from Examples 8-10 revealed that the carbonization atmosphere affects the catalytic effect of the catalyst. When the carbonization atmosphere is CO, the conversion rate of olefins and the selectivity of oxygen-containing compounds are optimal. When the carbonization atmosphere is a mixture of H2 and CO, the smaller the molar ratio of H2 / CO, the better the catalytic effect of the catalyst. This is mainly because different carbonization conditions directly affect the formation of alloy carbide phases, thereby directly affecting the catalytic performance of the catalyst.

[0164] 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 catalyst for the hydroformylation of olefins to prepare oxygen-containing compounds, characterized in that, The catalyst is Fe. x Co y M, wherein the catalyst contains C element, and the catalyst contains 1~10wt%C, 0.1~15wt%M, 85~98.9wt%Fe and Co, the atomic ratio of x to y is 0.1~10, and M is a metallic element selected from one or more of Li, Na, K, Rb and Cs.

2. The method for preparing the catalyst according to claim 1, characterized in that, It is prepared by co-precipitation using soluble salts of Fe and Co and precipitants containing M as raw materials.

3. The preparation method according to claim 2, characterized in that, The coprecipitation method is as follows: the solution of the soluble salts corresponding to Fe and Co is contacted with the precipitant solution to trigger a coprecipitation reaction, resulting in a precipitate, which is then calcined. And / or, the soluble salt corresponding to Fe is one or more selected from ferric chloride, ferric nitrate, ferric sulfate and ferric acetate; And / or, the soluble salt corresponding to Co is one or more selected from cobalt chloride, cobalt nitrate, cobalt sulfate and cobalt acetate; And / or, the precipitant containing M is selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, LiOH, NaOH, KOH, RbOH and CsOH; And / or, the catalyst is subjected to reduction or carbonization treatment.

4. The preparation method according to claim 3, characterized in that, The coprecipitation reaction temperature is 10~80 ℃; And / or, the calcination temperature is 300~600 ℃, and the calcination time is 2~10 h; And / or, the pH of the coprecipitation reaction system is 7~12; And / or, in the solution of the soluble salts corresponding to Fe and Co, the sum of the molar concentrations of Fe and Co elements is 0.1~2.0 mol / L; And / or, in the precipitant solution, the molar concentration of element M is 0.1~2.0 mol / L; And / or, before roasting, perform aging, centrifugation, washing, and drying treatments.

5. The preparation method according to claim 4, characterized in that, Includes one or more of the following features: The aging temperature is 20~80℃; The aging time is 0.5~10 h; Drying temperature: 50~120℃.

6. The preparation method according to claim 3, characterized in that, Includes one or more of the following features: The reduction temperature is 300~500 ℃; The reduction pressure is 0.1~1.0 MPa; Reduction time: 5-10 h; reduction space velocity: 1000-20000 h⁻¹ -1 ; The reducing atmosphere is hydrogen. The carbonization atmosphere is CO; Carbonization space velocity is 500~2000h -1 ; The carbonization pressure is 0.1~1.0 MPa; Carbonization time: 5~24 h; The carbonization temperature is 200~300℃.

7. The application of the catalyst as described in claim 1 in the preparation of oxygen-containing compounds by hydroformylation of olefins.

8. The application according to claim 7, characterized in that, The oxygen-containing compounds include alcohols, aldehydes, and acids.

9. The application according to claim 7, characterized in that, Includes one or more of the following features: The reaction temperature for the hydroformylation reaction is 100~200℃; The reaction pressure for the hydroformylation reaction is 1.0~6.0 MPa; The hydroformylation reaction system includes a feed gas, which is a mixture of H2 and CO in a molar ratio of 0.5 to 2.0; the hydroformylation reaction system also includes a solvent, which is one or more selected from cyclohexane, decane, undecane, and dodecane. The olefin is an α-olefin; The mass-to-volume ratio of the catalyst to the olefin is 10~200 mg / mL.

Images