Catalyst for preparing oxygen-containing compound through olefin hydroformylation reaction as well as preparation method and application of catalyst

Abstract

The invention provides a catalyst for preparing an oxygen-containing compound through olefin hydroformylation reaction and a preparation method and application thereof, the catalyst is FexCoyM, the catalyst contains 0.1-15 wt% of M, 85-99.9 wt% of Fe and Co, the atomic number ratio of x to y is 0.1-10, and M is a metal element. When the catalyst is used for preparing an oxygen-containing compound through olefin hydroformylation reaction, the conversion rate of olefin can reach 93-99.9%, and the selectivity of the oxygen-containing compound can reach 89-98.8%; and the catalyst is in a solid state in the reaction process, so that solid-liquid separation between the catalyst and the product is easy, and loss of the catalyst in the separation process is also avoided.

Description

Technical Field

[0001] The present invention relates to the technical field of catalyst preparation, and in particular to a catalyst for preparing oxygen-containing compounds through olefin hydroformylation reaction, and a preparation method and application thereof. Background Art

[0002] The hydroformylation reaction is the conversion of olefins into aldehydes or alcohols in the atmosphere of raw gas CO and H2. It is an important way to convert and utilize olefins with high added value. More than 10 million tons of olefins are converted to high value through this reaction pathway every year.

[0003] Various transition metal carbonyl complexes have catalytic effects on olefin hydroformylation reactions, but only cobalt and rhodium carbonyl complexes can be used for industrial production. The catalytically active body of the cobalt catalyst is tetracarbonyl hydrogen cobalt generated from dicobalt octacarbonyl. Dicobalt octacarbonyl is prepared by reacting metal cobalt, cobalt oxide, cobalt carbonate or cobalt fatty acid salt with raw gas CO and H2. Since dicobalt octacarbonyl is very easy to decompose even at room temperature, in order to obtain more tetracarbonyl hydrogen cobalt, the preparation process of the cobalt catalyst must be carried out under a higher CO partial pressure. In addition, the use of cobalt catalysts also has the problems of difficulty in catalyst recovery, low number of reusable times and equipment corrosion. Rhodium catalysts have high activity and good thermal stability, and the pressure requirements for the preparation process are not high. However, since the rhodium catalyst is in the same phase as the raw material and product, the separation and recovery of the catalyst after the reaction is inevitably accompanied by the loss of rhodium. This problem is particularly prominent due to the sharp rise in rhodium prices in recent years. Summary of the invention

[0004] In view of the above-mentioned shortcomings of the prior art, the object of the present invention is to provide a catalyst for preparing oxygen-containing compounds by hydroformylation of olefins, and a preparation method and use thereof, so as to obtain a catalyst having both the high activity and high selectivity of a homogeneous catalyst and the advantages of a supported solid catalyst, i.e., easy separation of the product and the catalyst.

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

[0006] The present invention provides a catalyst for preparing oxygen-containing compounds by olefin hydroformylation reaction, 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, M is a metal element, and 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] For example, the content of M element in the catalyst is 0.1-0.2wt%, 0.2-0.3wt%, 0.3-0.4wt%, 0.4-0.5wt%, 0.5-0.6wt%, 0.6-0.7wt%, 0.7-0.8wt%, 0.8-0.9wt%, 0.9-1.0wt%, 1.0-5wt%, 5-10wt% and 10-15wt%.

[0009] For example, the contents of Fe and Co in the catalyst are 85-90wt%, 90-92wt%, 90-95wt%, 95-97wt%, 97-98.9wt% and 98.9-99.9wt%.

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

[0011] Preferably, the catalyst comprises C element, and the catalyst contains 0.1-10 wt% M, 1-10 wt% C, 85-98.9 wt% Fe and Co.

[0012] For example, the content of C element in the catalyst is 1-2wt%, 2-3wt%, 3-5wt%, 5-7wt%, 7-9wt%, 9-10wt%.

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

[0014] Preferably, the co-precipitation method is as follows: a solution of soluble salts corresponding to Fe and Co is brought into contact with a precipitant solution to trigger a co-precipitation reaction to obtain a precipitate, and the precipitate is calcined.

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

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

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

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

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

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

[0021] More preferably, the calcination temperature is 300-600°C, preferably 350-400°C.

[0022] More preferably, the calcination time is 2 to 10 hours, 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 to 2.0 mol / L, and further preferably 1.0 to 2.0 mol / L.

[0024] More preferably, in the precipitant solution, the molar concentration of the M element 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, 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 one selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, LiOH, NaOH, KOH, RbOH and CsOH.

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

[0031] More preferably, the reduction temperature is 300 to 500°C, for example, 300 to 400, 400 to 500°C.

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

[0033] More preferably, the reduction time is 5 to 10 hours, such as 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 to 20000 h -1 .

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

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

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

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

[0039] More preferably, the carbonization time is 5 to 24 hours, such as 5 to 10 hours, 10 to 15 hours, 15 to 20 hours, 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] The present invention also provides the use of the catalyst as described above in the preparation of oxygen-containing compounds by olefin hydroformylation reaction.

[0042] Preferably, the oxygenates include alcohols, aldehydes and acids.

[0043] Preferably, the reaction temperature of the hydroformylation reaction is 100-200°C, such as 100-150°C, 150-180°C, or 180-200°C.

[0044] Preferably, the reaction time of the hydroformylation reaction is 1 to 20 hours, such as 1 to 10 hours, 10 to 20 hours.

[0045] Preferably, the reaction pressure of the hydroformylation reaction is 1.0-6.0 MPa, such as 1.0-2.0 MPa, 2.0-3.0 MPa, 3.0-4.0 MPa, 4.0-5.0 MPa, 5.0-6.0 MPa.

[0046] Preferably, the stirring speed is 500-2000 rpm, such as 500-1000 rpm, 1000-1500 rpm, or 1500-2000 rpm.

[0047] Preferably, the hydroformylation reaction system includes a raw material gas, which is a mixture of H2 and CO, and the molar ratio is 0.5 to 2.0, such as 0.5 to 1.0, 1.2 to 2.0.

[0048] Preferably, the hydroformylation reaction system comprises a solvent, and the solvent 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), more preferably 1:(9-15).

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

[0051] Preferably, the mass volume ratio of the catalyst to the olefin is 10-200 mg / mL, such as 10-100 mg / mL, 100-160 mg / mL, or 160-200 mg / mL.

[0052] The catalyst Fe disclosed in the present invention x Co y M is an alloy catalyst, which is pretreated before the olefin hydroformylation reaction, and carbon is introduced through carbonization treatment 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. When the catalyst is used in the hydroformylation reaction of olefins to prepare oxygen-containing compounds, the conversion rate of olefins can reach

[0055] 93~99.9%, the selectivity of oxygen-containing compounds can reach 89~98.8%;

[0056] 2. The catalyst is in solid state during the reaction, which makes it easy to separate the solid from the product and avoid the loss of the catalyst during the separation process;

[0057] 3. It is non-corrosive to the equipment and still shows 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] Figure 1 Shown is the XRD spectrum of the catalyst prepared in Example 6 of the present invention.

[0060] Figure 2Shown is the XRD spectrum of the catalyst prepared in Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0061] The following is a description of the implementation of the present invention by means of specific embodiments. Those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification.

[0062] Before further describing the 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 terms used in the examples of the present invention are intended to describe specific embodiments, rather than to limit the scope of protection of the present invention. The test methods in the following examples without specifying specific conditions are generally carried out under conventional conditions or under conditions recommended by the manufacturers.

[0063] When the embodiments give numerical ranges, it should be understood that, unless otherwise specified in the present invention, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as those generally understood by those skilled in the art. In addition to the specific methods, equipment, and materials used in the embodiments, according to the grasp of the prior art by those skilled in the art and the record of the present invention, any methods, equipment, and materials of the prior art similar or equivalent to the methods, equipment, and materials described in the embodiments of the present invention can also be used to realize the present invention.

[0064] In this embodiment, a specific catalyst for preparing oxygen-containing compounds by hydroformylation of olefins is provided. The catalyst 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, 1 to 10 wt% C, and 85 to 98.9 wt% Fe and Co. Wherein, M is one or more selected from Li, Na, K, Rb, and Cs.

[0065] The preparation method of the catalyst is as follows:

[0066] (1) A solution of soluble salts corresponding to Fe and Co and a precipitant solution are simultaneously dropped into water to trigger a co-precipitation reaction, thereby obtaining a precipitate. After aging, centrifugation, washing, drying, and calcination, a 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° C., and the pH of the coprecipitation reaction system is 6-12.

[0069] (2) The precursor is subjected to reduction and carbonization treatment to obtain the catalyst.

[0070] The reducing atmosphere is hydrogen, and the reducing space velocity is 1000~20000h -1 , the reduction pressure is 0.1-1.0MPa, the reduction temperature is 300-500℃, and the reduction time is 5-10h. After the reduction is completed, the temperature is lowered to the carbonization temperature, the carbonization temperature is 200-300℃, the carbonization atmosphere is switched to start the carbonization process, and the carbonization space velocity is maintained at 500-2000h -1 The carbonization pressure is 0.1-1.0 MPa and the carbonization time is 5-24 hours. The catalyst is obtained after the carbonization process is completed.

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

[0072] The catalyst is tableted, sieved and loaded into an intermittent small reactor, the particle size of the catalyst is 40-60 mesh, olefin and solvent are added, the volume ratio of the two is 1: (9-20), the mass volume ratio of the catalyst to the olefin is 1.0-20 mg / mL, a mixed gas with a H2 / CO molar ratio of 0.5-2.0 is introduced as a raw gas, the back pressure is increased to 1.0-6.0 MPa, the temperature is increased to 100-200°C, and a hydroformylation reaction is carried out to prepare oxygen-containing compounds. The stirring speed is 500-2000 rpm and the reaction time is 1-20 hours.

[0073] More specific embodiments are provided below for illustration.

[0074] Example 1

[0075] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 1:1, with the mass of Co element accounting for 50wt% of the mass of the catalyst and the mass of Na element accounting for 1.0wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 47% of the mass of the catalyst, recorded as 47Fe-50Co-C-1Na.

[0076] This embodiment also provides a method for preparing the above-mentioned catalyst, and the specific steps are as follows:

[0077] (1) Cobalt nitrate and iron nitrate were weighed so that Co accounted for 50% of the total mass of the catalyst and the Fe / Co molar ratio was 1:1, and dissolved in water to form a salt solution. In the salt solution, the total molar concentration of cobalt and iron was 1.0 mol / L. Na2CO3 was weighed so that the Na element accounted for 1.0% of the total mass of the catalyst and dissolved in water to form a Na2CO3 solution. In the Na2CO3 solution, the molar concentration of Na was 1.0 mol / L.

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

[0079] The pH value is 8.0, and the precipitate is obtained by filtration, and the precursor is obtained after aging, centrifugation, washing, drying and calcination.

[0080] The aging temperature is 50°C, the aging time is 2h, the number of centrifugation and washing is 5 times, the drying temperature is 120°C, the drying time is 24h, the roasting temperature is 400°C, and the roasting time is 4h.

[0081] (2) The precursor is subjected to reduction and carbonization treatment to obtain the catalyst.

[0082] The reducing atmosphere was pure H2, and the reduction was carried out at 400°C and 0.5 MPa for 5 h, with a reduction space velocity of 10,000 h -1 After the reduction, the temperature was lowered to 250 °C, and the carbonization atmosphere was switched to pure CO to start the carbonization process. The carbonization space velocity was maintained at 2000 h -1 The carbonization pressure was 0.5 MPa and the carbonization time was 10 h. The catalyst was obtained after the carbonization process.

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

[0084] The catalyst tablets were sieved, 100 mg of catalyst with a size of 40 to 60 mesh was weighed and loaded into a batch-type small reactor, 1-octene and cyclohexane were added, the total volume was 10 mL, the volume ratio of 1-octene to cyclohexane was 1:9, the mass volume ratio of catalyst to 1-octene was 100 mg / mL, a mixed gas with a molar ratio of H2 / CO of 1 was introduced as the raw gas, the back pressure was increased to 4 MPa, the temperature was raised to 150°C, the magnetic speed was 1000 rpm, and the hydroformylation reaction was carried out to prepare oxygen-containing compounds, and the reaction time was 10 hours. The catalytic results are shown in Table 1.

[0085] Example 2

[0086] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 1:1, with the mass of Co element accounting for 47wt% of the mass of the catalyst and the mass of Na element accounting for 1.0wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 45% of the mass of the catalyst, recorded as 45Fe-47Co-C-1Na.

[0087] This embodiment also provides a method for preparing the above-mentioned catalyst, and the preparation method is different from that of Example 1 only in that: cobalt chloride and ferric chloride are weighed according to Co accounting for 47wt% of the total amount of the catalyst and Fe / Co molar ratio is 1:1, and 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 Na element accounting for 1.0wt% of the total amount of the catalyst and dissolved in water to form a Na2CO3 solution, in which the molar concentration of Na is 1.0 mol / L.

[0088] The carbonization temperature was 250°C, the carbonization atmosphere was pure CO, and the carbonization space velocity was maintained at 2000 h -1 , the carbonization pressure is 0.8 MPa, and the carbonization time is 20 h. Other preparation steps are the same as those in Example 1.

[0089] This example also provides the above-mentioned catalyst for olefin hydroformylation reaction to prepare oxygen-containing compounds, and the preparation method is the same as that of Example 1. The catalytic results are shown in Table 1.

[0090] Example 3

[0091] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to an atomic ratio of x to y of 3:1, with the mass of Co element accounting for 23wt% of the mass of the catalyst and the mass of Na element accounting for 1.0wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 74% of the mass of the catalyst, recorded as 74Fe3-23Co-C-1Na.

[0092] This embodiment also provides a method for preparing the above-mentioned catalyst, which differs from that of Example 1 only in that cobalt chloride and ferric chloride are weighed according to Co accounting for 23wt% of the total catalyst and Fe / Co molar ratio of 3:1, and dissolved in water to form a salt solution, in which the total molar concentration of cobalt and iron is 1.0 mol / L. The other preparation steps are the same as those of Example 1.

[0093] This embodiment also provides the above-mentioned catalyst for use in olefin hydroformylation reaction to prepare oxygen-containing compounds, and the preparation method is the same as that in Example 1.

[0094] Example 4

[0095] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 1:2, with the mass of Co element accounting for 66wt% of the mass of the catalyst and the mass of Na element accounting for 1.0wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 31% of the mass of the catalyst, recorded as 31Fe-66Co2-C-1Na.

[0096] This embodiment also provides a method for preparing the above-mentioned catalyst, which differs from that of Example 1 only in that cobalt chloride and ferric chloride are weighed according to a ratio of 66 wt% of Co to the total catalyst and a molar ratio of Fe / Co of 1:2, and dissolved in water to form a salt solution, wherein the total molar concentration of cobalt and iron in the salt solution is 1.0 mol / L. The other preparation steps are the same as those of Example 1.

[0097] This example also provides the above-mentioned catalyst for olefin hydroformylation reaction to prepare oxygen-containing compounds, and the preparation method is the same as that of Example 1. The catalytic results are shown in Table 1.

[0098] Example 5

[0099] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 1:2, with the mass of Co element accounting for 66wt% of the mass of the catalyst and the mass of K element accounting for 1.0wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 31% of the mass of the catalyst, and is recorded as 31Fe-66Co2-C-1K.

[0100] This embodiment also provides a method for preparing the above-mentioned catalyst, which differs from that of Example 4 only in that K2CO3 is weighed and dissolved in water to prepare a K2CO3 solution according to the K element accounting for 1.0wt% of the total amount of the catalyst, and the molar concentration of the K element in the K2CO3 solution is 1.0mol / L. The other preparation steps are the same as those of Example 4.

[0101] This example also provides the above-mentioned catalyst for olefin hydroformylation reaction to prepare oxygen-containing compounds, and the preparation method is the same as that of Example 4. The catalytic results are shown in Table 1.

[0102] Example 6

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

[0104] This embodiment also provides the above-mentioned catalyst for olefin hydroformylation reaction to prepare oxygen-containing compounds. The preparation method is different from that of Example 1 only in that 1-decene is used to replace 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 volume ratio of the catalyst to 1-decene is 160 mg / mL, the reaction temperature is 180°C, and the other preparation steps are the same as those of Example 1. The catalytic results are shown in Table 1.

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

[0106] This embodiment also provides a life test of the above-mentioned catalyst.

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

[0108] Example 7

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

[0110] This example also provides the above-mentioned catalyst for olefin hydroformylation reaction to prepare oxygen-containing compounds, and the reaction process is different from that of Example 6 only in that: 1-decene and cyclohexane are added, the total volume is 10 mL, the volume ratio of 1-decene to cyclohexane is 1:9, the mass volume ratio of the catalyst to 1-octene is 100 mg / mL, and the other steps are the same as those of Example 6. The catalytic results are shown in Table 1.

[0111] Example 8

[0112] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 2:1, with the mass of Co element accounting for 33.5wt% of the mass of the catalyst and the mass of Na element accounting for 1.0wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 63.5% of the mass of the catalyst, recorded as 63.5Fe2-33.5Co-C-1Na.

[0113] This embodiment also provides a method for preparing the above-mentioned catalyst, and the specific steps are as follows:

[0114] (2) Cobalt chloride and ferric chloride were weighed so that Co accounted for 33.5% of the total mass of the catalyst and the Fe / Co molar ratio was 2:1, and dissolved in water to form a salt solution. The total molar concentration of cobalt and iron in the salt solution was 1.0 mol / L. Na2CO3 was weighed so that the Na element accounted for 1.0% of the total mass of the catalyst and dissolved in water to form a Na2CO3 solution.

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

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

[0117] The pH value is 8.0, and the precipitate is obtained by filtration, and the precursor is obtained after aging, centrifugation, washing, drying and calcination.

[0118] The aging temperature is 50°C, the aging time is 2h, the centrifugation and washing times are 5 times, the drying temperature is 120°C, the drying time is 24h, the calcination temperature is 400°C, and the calcination time is 4h.

[0119] (2) The precursor is subjected to reduction and carbonization treatment to obtain the catalyst.

[0120] The reducing atmosphere was pure H2, and the reduction was carried out at 400°C and 0.5 MPa for 5 h, with a reduction space velocity of 10,000 h -1 After the reduction, the temperature was lowered to 250 °C, and the carbonization atmosphere was switched to start the carbonization process. The carbonization atmosphere was a mixture of H2 / CO with a molar ratio of 1:1, and the carbonization space velocity was maintained at 2000 h -1 The carbonization pressure was 0.5 MPa and the carbonization time was 10 h. The catalyst was obtained after the carbonization process.

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

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

[0123] Example 9

[0124] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 2:1, with the mass of Co element accounting for 33.5wt% of the mass of the catalyst and the mass of Na element accounting for 1.0wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 63.5% of the mass of the catalyst, recorded as 63.5Fe2-33.5Co-C-1Na.

[0125] This embodiment also provides a method for preparing the above-mentioned catalyst, and the preparation method is different from that of Example 8 only in that the carbonization atmosphere is CO; the other preparation steps are the same.

[0126] This example also provides the above-mentioned catalyst for olefin hydroformylation reaction to prepare oxygen-containing compounds, and the preparation method is the same as that of Example 8. The catalytic results are shown in Table 1.

[0127] Example 10

[0128] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 2:1, with the mass of Co element accounting for 33.5wt% of the mass of the catalyst and the mass of Na element accounting for 1.0wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 63.5% of the mass of the catalyst, recorded as 63.5Fe2-33.5Co-C-1Na.

[0129] This embodiment also provides a method for preparing the above-mentioned catalyst, and the preparation method is different from that of Example 9 only in that the carburizing atmosphere is a mixture of H2 / CO in a molar ratio of 2:1; the other preparation steps are the same.

[0130] This example also provides the above-mentioned catalyst for olefin hydroformylation reaction to prepare oxygen-containing compounds, and the preparation method is the same as that of Example 9. The catalytic results are shown in Table 1.

[0131] Embodiment 11

[0132] This embodiment provides a more specific catalyst, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 1:1, with the mass of Co element accounting for 47wt% of the mass of the catalyst and the mass of Na element accounting for 0.3wt% of the mass of the catalyst, wherein the mass of Fe element accounts for 45% of the mass of the catalyst, recorded as 45Fe-47Co-C-0.3Na.

[0133] This embodiment also provides a method for preparing the above-mentioned catalyst, which differs from the method in Example 1 only in that: Co nitrate and ferric nitrate are weighed according to the ratio of Co to 47% of the total mass of the catalyst and the molar ratio of Fe / Co is 1:1, and 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 ratio of Na element to 0.3% of the total mass of the catalyst and dissolved in water to form a Na2CO3 solution, in which the molar concentration of Na is 1.0 mol / L. The other preparation methods are the same.

[0134] This example also provides the above-mentioned catalyst for olefin hydroformylation reaction to prepare oxygen-containing compounds, and the preparation method is the same as that of 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, which contains a carbide layer and is prepared according to the atomic ratio of x to y being 1:1, with the mass of Co element accounting for 50wt% of the mass of the catalyst and the mass of Na element accounting for 1.0wt% of the mass of the catalyst, wherein the Fe element content is 47%, recorded as 47Fe-50Co-C-1Na.

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

[0138] This comparative example also provides the above-mentioned catalyst for the hydroformylation reaction of olefins to prepare oxygen-containing compounds, and the preparation method is the same as that of Example 1.

[0139] Figure 2 3 is the XRD spectrum of the catalyst prepared in Comparative Example 1. It can be seen from the XRD spectrum that the characteristic diffraction 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, wherein the catalyst contains a carbide layer, and is prepared according to the ratio of the number of atoms of x to y being 1:15, the mass of the Co element accounting for 94wt% of the mass of the catalyst, and the mass of the Na element accounting for 1.0wt% of the mass of the catalyst, wherein the Fe element content is 6%, and is recorded as 6Fe-94Co 10 -C-1Na.

[0142] This embodiment also provides a method for preparing the catalyst described above, which differs from that of Example 1 only in that cobalt nitrate and iron nitrate are weighed according to the ratio of Co to 94wt% of the total catalyst and the molar ratio of Fe / Co being 1:15, and dissolved in water to form a salt solution, wherein the total molar concentration of cobalt and iron in the salt solution is 1.0 mol / L. The other preparation steps are the same as those of Example 1.

[0143] This comparative example also provides the above-mentioned catalyst for the hydroformylation reaction of olefins to prepare oxygen-containing compounds, and the preparation method is the same as that of 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, wherein the catalyst contains a carbide layer, and is prepared according to the ratio of the number of atoms of x to y being 15, the mass of the Co element accounting for 6.6wt% of the mass of the catalyst, the mass of the Na element accounting for 1.0wt% of the mass of the catalyst, wherein the Fe element content is 93.4%, recorded as 93.4Fe 15 -6.6Co-C-1Na.

[0146] This embodiment also provides a method for preparing the above-mentioned catalyst, which differs from that of Example 1 only in that cobalt chloride and ferric chloride are weighed according to a ratio of Co to 6.6wt% of the total catalyst and a molar ratio of Fe / Co of 15, and dissolved in water to form a salt solution, wherein the total molar concentration of cobalt and iron in the salt solution is 1.0mol / L. The other preparation steps are the same as those of Example 1.

[0147] This comparative example also provides the above-mentioned catalyst for the hydroformylation reaction of olefins to prepare oxygen-containing compounds, and the preparation method is the same as that of 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, which contains a carbide layer and is prepared according to an Fe and Co content of 80wt%, an atomic ratio of x to y of 1:1, and a Na element mass accounting for 1.0wt% of the catalyst mass, wherein the Co element content is 41wt%, the Fe element content is 39wt%, and is recorded as 39Fe-41Co-C-1Na.

[0150] This embodiment also provides a method for preparing the above-mentioned catalyst, which differs from that of Example 1 only in that cobalt nitrate and iron nitrate are weighed according to the ratio of Co to 41wt% of the total catalyst and the molar ratio of Fe / Co is 1:1, and dissolved in water to form a salt solution, in which the total molar concentration of cobalt and iron is 1.0 mol / L. The other preparation steps are the same as those of Example 1.

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

[0152] Table 1

[0153]

[0154]

[0155] Table 2

[0156]

[0157] From Table 2, we can see that:

[0158] According to the data comparison of Example 1, Example 2 and Comparative Example 4, it was found that when the Fe / Co content was increased from 92% to 97%, the conversion rate of olefins increased from 98.6% to 99.7%, and the selectivity of oxygen-containing compounds increased from 91.0% to 91.7%, indicating that as the Fe / Co content increased, the conversion rate of olefins and the selectivity of oxygen-containing compounds gradually increased.

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

[0160] According to the data comparison of Example 1 and Examples 3 to 4 and Comparative Examples 2 to 3, it is found that when the Fe / Co molar ratio is 1:1, the conversion rate of olefins and the selectivity of oxygen-containing compounds are optimal; when the Fe / Co molar ratio increases or decreases, the conversion rate of olefins and the selectivity of oxygen-containing compounds are reduced; if the Fe / Co molar ratio increases to a large value, such as 15, or the Fe / Co molar ratio decreases to a small value, such as 1:15, the conversion rate of olefins and the selectivity of oxygen-containing compounds are greatly reduced.

[0161] According to the data comparison of Examples 1 and 7, it is found that the higher the reaction temperature, the higher the conversion rate of olefins and the selectivity of oxygen-containing compounds.

[0162] According to the data comparison between Examples 1 and 6, it is found that the conversion rate of olefins and the selectivity of oxygen-containing compounds are improved when the mass volume ratio of catalyst to olefin is increased from 100 mg / mL to 160 mg / mL.

[0163] According to the data comparison of Examples 8 to 10, it was found 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 / 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 the alloy carbide phase, 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 present invention. Anyone familiar with the art may 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 a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A catalyst for preparing oxygen-containing compounds by hydroformylation of olefins, characterized in that: 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.

2. The catalyst according to claim 1, characterized in that M is one or more selected from Li, Na, K, Rb, and Cs; and / or, the catalyst includes the element C, and the catalyst contains 0.1-10wt% M, 1-10wt% C, 85-98.9wt% Fe and Co.

3. The method for preparing the catalyst according to any one of claims 1 to 2, characterized in that: The method is prepared by using a co-precipitation method, with soluble salts corresponding to Fe and Co and a precipitant containing M as raw materials.

4. The preparation method according to claim 3, characterized in that: The co-precipitation method comprises: contacting a solution of soluble salts corresponding to Fe and Co with a precipitant solution to trigger a co-precipitation reaction to obtain a precipitate, and calcining the precipitate; 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 one selected from Li2CO3, Na2CO3, K2CO3, Rb2CO3, Cs2CO3, LiOH, NaOH, KOH, RbOH and CsOH; And / or, the catalyst is subjected to reduction and carbonization treatment.

5. The preparation method according to claim 4, characterized in that: The coprecipitation reaction temperature is 10-80°C; and / or, a calcination temperature of 300 to 600° C. and a calcination time of 2 to 10 hours; and / or, the pH of the coprecipitation reaction system is 7 to 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 to 2.0 mol / L; and / or, in the precipitant solution, the molar concentration of the M element is 0.1 to 2.0 mol / L; And / or, before roasting, aging, centrifugation, washing and drying are performed.

6. The preparation method according to claim 5, characterized in that: Include one or more of the following characteristics: Aging temperature is 20~80℃; Aging time is 0.5 to 10 hours; Drying temperature is 50~120℃.

7. The preparation method according to claim 4, characterized in that: Includes one or more of the following features: The reduction temperature is 300-500°C; The reduction pressure is 0.1~1.0MPa; Reduction time 5 to 10 hours; Reduction space velocity is 1000~20000h -1 ; The reducing atmosphere is hydrogen; The carbonization atmosphere is CO; Carbonization space velocity is 500~2000h -1 ; Carbonization pressure is 0.1~1.0MPa; Carbonization time 5 to 24 hours; The carbonization temperature is 200-300°C.

8. Use of the catalyst according to any one of claims 1 to 2 in the preparation of oxygen-containing compounds by olefin hydroformylation reaction.

9. The use according to claim 8, characterized in that: The oxygenates include alcohols, aldehydes and acids.

10. The use according to claim 8, characterized in that: Includes one or more of the following features: The reaction temperature of the hydroformylation reaction is 100-200°C; The reaction pressure of the hydroformylation reaction is 1.0 to 6.0 MPa; The hydroformylation reaction system includes a raw material gas, which is a mixture of H2 and CO with a molar ratio of 0.5 to 2.0; the hydroformylation reaction system includes a solvent, which is one or more selected from cyclohexane, decane, undecane and dodecane; The olefin is an α-olefin; The mass volume ratio of the catalyst to the olefin is 10 to 200 mg / mL.

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