Method for preparing oxygen-containing organic compounds via hydromethionization

Abstract

A method for preparing oxygen-containing organic compounds via hydromethionization is disclosed, comprising: 1) in the presence of a hydromethionization catalyst and at a first reaction temperature, contacting an organic compound having 2-60 carbon atoms and at least one carbon-carbon double bond with syngas to undergo hydromethionization, obtaining a reaction mixture containing the oxygen-containing organic compound and a heavy component, wherein the first reaction temperature is 60-150°C; and 2) in the presence of syngas and at a second reaction temperature, continuing the reaction mixture obtained in step 1) to decompose the heavy component, obtaining a reaction product with a reduced content of the heavy component and an increased content of the oxygen-containing organic compound, wherein the second reaction temperature is 20-100°C higher than the first reaction temperature. This method can achieve reduced alkane selectivity and increased alcohol selectivity; and can reduce the content of heavy components in the product, significantly reducing the amount of waste material discharged and reducing waste liquid emissions, which is beneficial to environmental protection and has industrialization prospects.

Description

Technical Field

[0001] This application relates to the field of hydromethionization reactions, and more specifically to a method for preparing oxygen-containing organic compounds via hydromethionization reactions. Prior Technology

[0002] Organic compounds with carbon-carbon double bonds, such as alkenes, can undergo hydromethionization with carbon monoxide and hydrogen in the presence of a catalyst to yield aldehydes and / or alcohols with an additional carbon atom. Traditional hydromethionization methods involve reacting an unsaturated alkene with carbon monoxide and hydrogen in the presence of a catalyst under specific reaction conditions to produce one or more aldehydes and / or alcohols. In industrial production, the catalysts used for hydromethionization reactions are generally cobalt (Co)-based or rhodium (Rh)-based catalysts.

[0003] CN102123978A discloses a method for hydrogenating and benzylating α-olefins to produce two or more aldehydes comprising a normal aldehyde and one or more isoaldehydes, wherein the target molar ratio of the normal aldehyde to one or more isoaldehydes is in a selectable range of 3 / 1 to 60 / 1. The method uses a transition metal-coordination complex catalyst comprising a symmetrical calixareline diphosphite ligand.

[0004] CN108586219A discloses a method for preparing aldehydes via the hydromethionization reaction of olefins. The preparation method is as follows: Step 1: In a first reactor, C2-C4 olefins are continuously prepared into aldehydes via hydromethionization with carbon monoxide and hydrogen under the action of a catalyst, with the temperature at 90℃ and the pressure at 2.5 MPa; Step 2: In a second reactor, heating is performed at a temperature of 70-80℃, while an inert gas is introduced into the second reactor; Step 3: The first reactor and the second reactor are connected, and the aldehyde prepared in the first reactor is introduced into the second reactor; Step 4: During the introduction in step 3, it is carried out under isobaric but unequal temperature conditions, and a secondary introduction is performed after the initial introduction. This technology involves a complex reaction process and uses a rhodium-phosphine complex catalyst, which is expensive.

[0005] Compared to cobalt catalysts, rhodium complexes exhibit higher reactivity and can react under milder temperatures and pressures. However, rhodium catalysts have poor high-temperature performance, making their application in the carbonylation of advanced olefins challenging. Existing rhodium catalysts show good catalytic performance for terminal olefins, but poor activity for internal olefins. The catalysts are oil-soluble, and product separation is difficult, leading to complex post-processing. Furthermore, rhodium is a rare and expensive precious metal, resulting in high recycling and reuse costs.

[0006] CN1370137A discloses a continuous method for the hydrogenation and methylation of olefins having 6-20 carbon atoms, wherein: a) an aqueous solution of cobalt(II) salt is thoroughly contacted with hydrogen and carbon monoxide to form an active cobalt catalyst for hydrogenation and methylation; then, an aqueous phase containing the cobalt catalyst is thoroughly contacted with the olefin and optionally an organic solvent, as well as hydrogen and carbon monoxide, in at least one reaction zone, whereby the cobalt catalyst is extracted into the organic phase and the olefin is hydrogenated and methylated; b) the effluent from the reaction zone is treated with oxygen in the presence of an acidic aqueous solution of cobalt(II) salt, wherein the cobalt catalyst decomposes to form cobalt(II) salt and these substances are stripped into the aqueous phase; and subsequently, the phases are separated; c) the aqueous solution of cobalt(II) salt is recycled to step a) in an unchanged form. This method has a complex process.

[0007] In the hydromethionization reaction, high alkane selectivity reduces the economic efficiency of the plant. Reducing alkane selectivity and increasing alcohol and aldehyde selectivity can improve the plant's economic efficiency. Reducing the content of heavy substances in the reaction products can reduce the amount of heavy materials discharged from the plant and reduce the amount of waste liquid discharged from the plant, which is beneficial to environmental protection. The amount of discharged materials also determines the industrial implementation prospects of the hydromethionization process.

[0008] Therefore, there is still a need for a method that can convert organic compounds with carbon-carbon double bonds into target aldehydes and / or alcohols in a low-cost and efficient manner. Summary of the Invention

[0009] The purpose of this application is to provide an improved method for preparing oxygen-containing organic compounds via hydromethionization, which achieves reduced alkane selectivity and increased alcohol and aldehyde selectivity.

[0010] To achieve the above objectives, this application provides a method for preparing oxygen-containing organic compounds via hydromethionization, comprising the following steps:

[0011] 1) In the presence of a hydromethionization catalyst and at a first reaction temperature, an organic compound having 2-60 carbon atoms and at least one carbon-carbon double bond is contacted with syngas containing CO and H₂ to undergo a hydromethionization reaction, yielding a reactant comprising the oxygen-containing organic compound and a heavy material, wherein the oxygen-containing organic compound is an alcohol, aldehyde, or a combination thereof that has one more carbon atom than the organic compound having a carbon-carbon double bond, and the first reaction temperature is 60-150°C; and

[0012] 2) In the presence of syngas containing CO and H2 and at a second reaction temperature, the reactants obtained in step 1) are allowed to continue reacting, causing the heavy substances therein to decompose, to obtain a reaction product with a reduced content of the heavy substances and an increased content of the oxygen-containing organic compounds, wherein the second reaction temperature is 140-200°C and the second reaction temperature is 20-100°C higher than the first reaction temperature.

[0013] Compared with existing methods, the method of this application can achieve reduced alkane selectivity and increased alcohol selectivity; and can reduce the content of heavy substances in the product, thereby significantly reducing the amount of waste material discharged and reducing waste liquid discharge, which is beneficial to environmental protection.

[0014] Meanwhile, the method of this application has a simple process flow, can be implemented continuously, has a high raw material conversion rate, a high target product yield, low alkane selectivity, and low waste discharge, and has good prospects for industrial application.

[0015] Other features and advantages of the present invention will be described in detail in the following detailed description section. Simple Explanation of the Diagram

[0016] none Implementation

[0017] The present application will be further described in detail below through specific embodiments. It should be understood that the specific embodiments described herein are only for illustration and explanation of the present application, and do not limit the present application in any way.

[0018] Any specific numerical value disclosed herein (including the endpoints of a numerical range) is not limited to the exact value of that value, but should be understood to also include values ​​close to that exact value. Furthermore, with respect to the disclosed numerical range, one or more new numerical ranges can be obtained by arbitrarily combining the endpoint values ​​of the range, the endpoint values ​​with specific point values ​​within the range, and the specific point values, and these new numerical ranges should also be considered as specifically disclosed herein.

[0019] Unless otherwise stated, the terms used herein have the same meaning as commonly understood by those skilled in the art, and if a term is defined herein and its definition differs from the common understanding in the art, the definition herein shall prevail.

[0020] In this application, the term "olefin" has the meaning commonly understood in the art, namely, an unsaturated hydrocarbon compound having a carbon-carbon double bond (C=C bond). The olefin can be a chain olefin or a cyclic olefin, and the number of its carbon-carbon double bonds can be one (i.e., a monoolefin), two (i.e., a diene), or more. The carbon-carbon double bonds can be at the end of the carbon chain (i.e., a terminal olefin, such as an α-olefin) or in the middle of the carbon chain (i.e., an inner olefin). Furthermore, the olefin may contain other functional groups, such as hydroxyl groups, aromatic rings, etc. In the method of this application, the olefin is preferably a monoolefin, more preferably a straight-chain or branched monoolefin.

[0021] In this application, "C8" refers to having 8 carbon atoms, and similarly, "C9" refers to having 9 carbon atoms.

[0022] In this application, the term "C8 olefin" refers to an olefin compound having 8 carbon atoms, preferably a straight-chain or branched monoolefin having 8 carbon atoms, including 1-octene and its various isomers, such as 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, 3,4,4-trimethyl-2-pentene, 2,3,3-trimethyl-1-pentene, 5,5-dimethyl-2-hexene, 3,5-dimethyl-2-hexene, 2,4-dimethyl-2-hexene, 2,3-dimethyl-3-hexene, 3,4-dimethyl-2-hexene, etc.

[0023] In this application, the term "hydromethoxylation catalyst" refers to various catalysts suitable for catalyzing the hydromethoxylation reaction to produce aldehydes. Such catalysts are well known in the art, such as the catalyst mentioned in Chinese Patent Application Publication CN106103399A, the contents of which are incorporated herein by reference in their entirety.

[0024] In this application, the term "organic phosphorus-containing ligand" has the meaning commonly understood in the art, specifically referring to a ligand whose molecular structure contains phosphorus and a group selected from hydrocarbon groups, hydroxyl groups, heterocyclic groups, or combinations thereof bonded to phosphorus. The hydrocarbon group and hydroxyl group can be various aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups, such as alkyl, cycloalkyl, and aryl groups. The heterocyclic group can be various organic groups having one or more heteroatoms selected from O, N, S, etc., in the ring. The group may also optionally have various substituents that do not adversely affect the properties of the resulting complex, such as sulfonic acid groups, halogen groups, amino groups, nitro groups, hydroxyl groups, carbonyl groups, etc. For example, the organic phosphorus-containing ligand can be a ligand whose molecular structure contains phosphorus and a hydrocarbon group bonded to phosphorus via a "PC" bond and / or a hydroxyl group bonded to phosphorus via a "PO" bond. Specific examples of the organic phosphorus-containing ligand include various phosphine ligands known in the art, particularly phosphine ligands having alkyl, aryl, and / or heterocyclic groups, such as trialkylphosphine ligands. Preferably, the organic phosphorus-containing ligand has the general formula PR 3, wherein each group R is independently selected from hydrocarbon groups, alkyl groups, and heterocyclic groups, and preferably independently selected from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, and aryloxy groups. The group R may also optionally have various substituents that do not adversely affect the properties of the resulting complex, such as sulfonic acid groups, halogen groups, amino groups, nitro groups, hydroxyl groups, carbonyl groups, etc. Examples of the organic phosphorus-containing ligand include, but are not limited to, phosphite ligands, triarylphosphine ligands, trialkylphosphine ligands, and alkylarylphosphine ligands, such as triphenylphosphine ligands, tributylphosphine ligands, tritert-butylphosphine ligands, tricyclohexylphosphine ligands, dibutyldiphenylphosphine ligands, ditert-butylneoptiylphosphine ligands, trioctylphosphine ligands, etc.

[0025] In this application, the term "cobalt-phosphine complex" refers to various cobalt complexes containing organic phosphorus-containing ligands, as defined above. For example, the cobalt-phosphine complex may be a cobalt complex containing various phosphine ligands known in the art (e.g., triphenylphosphine ligands, tributylphosphine ligands, tritert-butylphosphine ligands, etc.). In particular, when used as a hydromethionization catalyst, the cobalt-phosphine complex preferably also contains a carbonyl ligand in addition to the organic phosphorus-containing ligand.

[0026] In this application, the term "organophosphorus-containing coordination compound" refers to a compound that can be reacted with a metal source to yield a metal complex containing a metal and the aforementioned organic phosphorus-containing coordination group.

[0027] In this application, the term "heavy product" refers to the product obtained by further reaction between the oxygen-containing organic compounds or between the oxygen-containing organic compounds and other compounds, particularly the reaction product derived from at least two molecules of the oxygen-containing organic compounds, i.e., the reaction product obtained by at least two molecules of the oxygen-containing organic compounds through one or more chemical reaction processes, such as acetal compounds, hydroxyaldehyde compounds, ether compounds, ester compounds, or combinations thereof obtained through aldol condensation, acetalization, etherification, oxidation, and esterification reactions. For example, when using C8 olefins as raw materials, the heavy product may be an acetal compound, hydroxyaldehyde compound, ether compound, ester compound, or combination thereof obtained by at least two molecules of C9 aldehydes and / or C9 alcohols through one or more chemical reaction processes.

[0028] In this application, except where expressly stated, any matters or issues not mentioned herein shall be directly applicable to those known in the art without any modification. Furthermore, any implementation described herein may be freely combined with one or more other implementations described herein, and the resulting technical solutions or concepts shall be considered part of the original disclosure or original record of this application, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be clearly unreasonable.

[0029] All patent and non-patent literature mentioned in this article, including but not limited to textbooks and journal articles, are incorporated in full by way of citation.

[0030] As described above, this application provides a method for preparing oxygen-containing organic compounds via hydromethionization, comprising the following steps:

[0031] 1) In the presence of a hydromethionization catalyst and at a first reaction temperature, an organic compound having 2-60 carbon atoms and at least one carbon-carbon double bond is contacted with syngas containing CO and H₂ to undergo a hydromethionization reaction, yielding a reactant comprising the oxygen-containing organic compound and a heavy material, wherein the oxygen-containing organic compound is an alcohol, aldehyde, or a combination thereof that has one more carbon atom than the organic compound having a carbon-carbon double bond, and the first reaction temperature is 60-150°C; and

[0032] 2) In the presence of syngas containing CO and H2 and at a second reaction temperature, the reactants obtained in step 1) are allowed to continue reacting, causing the heavy substances therein to decompose, to obtain a reaction product with a reduced content of the heavy substances and an increased content of the oxygen-containing organic compounds, wherein the second reaction temperature is 140-200°C and the second reaction temperature is 20-100°C higher than the first reaction temperature.

[0033] In a preferred embodiment, the first reaction temperature in step 1) is 100-145°C, the second reactant temperature in step 2) is 170-200°C, and the second reaction temperature is 30-70°C higher than the first reaction temperature, preferably 40-60°C higher.

[0034] The inventors of this application discovered in their research that, according to the two-stage reaction process of this application, the hydromethionization reaction in step 1) is carried out at a lower temperature and in the presence of syngas. While generating the target oxygen-containing organic compound, it also produces a heavy substance formed by at least two molecules of the oxygen-containing organic compound through one or more chemical reaction processes. The reaction in step 2) is carried out at a higher temperature and in the presence of syngas, which can cause the heavy substance to decompose back into the target oxygen-containing organic compound. The by-product alkane does not increase significantly during the reaction in step 2), thereby significantly reducing the content of heavy substance in the final product, reducing alkane selectivity and increasing alcohol selectivity.

[0035] In a preferred embodiment, the reaction conditions in step 1) include: a reaction temperature of 60-150°C, preferably 100-145°C, more preferably 100°C to less than 130°C; a reaction pressure of 1-12 MPa, preferably 2-10 MPa; and a reaction time of 1-60 h, preferably 2-25 h.

[0036] In a preferred embodiment, the reaction conditions in step 2) include: a reaction temperature of 140-200°C, preferably 170-200°C; a reaction pressure of 1-12 MPa, preferably 2-10 MPa; and a reaction time of 1-40 h, preferably 2-25 h.

[0037] In some preferred embodiments, the molar ratio of the synthesis gas to the organic compound having carbon-carbon double bonds in step 1) of the method of this application is (0.1-12):1, preferably (3-6):1, wherein the molar amount of the synthesis gas is the sum of the molar amounts of each gas in the synthesis gas.

[0038] In a particularly preferred embodiment, steps 1) and 2) are carried out under a syngas atmosphere. In this case, the amounts of CO and H₂ in the reaction system are in significant excess relative to the reaction requirements.

[0039] In a preferred embodiment, the reaction time in step 1) is longer than the reaction time in step 2). More preferably, the reaction temperature in step 1) is below 130°C, thereby further reducing alkane selectivity.

[0040] In this application, there are no particular limitations on the hydromethionization catalyst, as long as it can effectively catalyze the hydromethionization of organic compounds with carbon-carbon double bonds to produce aldehydes. In a preferred embodiment, the hydromethionization catalyst is a transition metal complex catalyst suitable for catalyzing the hydromethionization reaction of olefins.

[0041] In a further preferred embodiment, the transition metal in the transition metal complex is selected from Group VIII metals, more preferably from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru) or combinations thereof, even more preferably from rhodium, cobalt, or combinations thereof, and particularly preferably from cobalt.

[0042] In a further preferred embodiment, the transition metal complex comprises a carbonyl ligand, an organophosphorus ligand, or a combination thereof, wherein the organophosphorus ligand is as defined above. Preferably, the organophosphorus ligand has the general formula PR 3, wherein each group R is independently selected from hydrocarbon groups, alkyl groups, and heterocyclic groups, and preferably independently selected from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, and aryloxy groups. The group R may also optionally have various substituents that do not adversely affect the properties of the resulting complex, such as sulfonic acid groups, halogen groups, amino groups, nitro groups, hydroxyl groups, carbonyl groups, etc. Particularly preferably, the organic phosphorus-containing ligand is selected from phosphite ligands, triarylphosphine ligands, trialkylphosphine ligands, alkylarylphosphine ligands, or combinations thereof, for example selected from triphenylphosphine ligands, tributylphosphine ligands, tritert-butylphosphine ligands, tricyclohexylphosphine ligands, dibutyldiphenylphosphine ligands, ditert-butylneopentylphosphine ligands, trioctylphosphine ligands, or combinations thereof.

[0043] In a preferred embodiment of the method of this application, the hydromethionization catalyst is used in the form of a solution of the transition metal complex in an organic solvent, wherein the mass concentration of the transition metal in the solution is preferably 0.01-3%, more preferably 0.2-2%. In this application, there are no particular limitations on the organic solvent, as long as it can dissolve the transition metal complex and does not adversely affect the hydromethionization reaction. Preferably, the organic solvent is selected from alkanes, aromatics, alcohols, ethers, aldehydes, ketones, nitriles, esters, or combinations thereof, more preferably from alcohols, aldehydes, or combinations thereof, and particularly preferably from alcohols or aldehydes having the same number of carbon atoms as the oxygen-containing organic compound that is the target product.

[0044] In a further preferred embodiment, the transition metal complex is a cobalt complex containing an organic phosphorus-containing coordinating group (also referred to herein as a "cobalt-phosphine complex"), and the hydromethionization catalyst is used in the form of a solution of the cobalt complex. Preferably, the mass concentration of cobalt in the cobalt complex solution is 0.01-3%, more preferably 0.2-2%, and more preferably 0.3-1.5%, wherein the mass concentration of cobalt = (mass of cobalt / mass of catalyst solution) × 100%; more preferably, the mass ratio of cobalt to phosphorus in the cobalt complex solution is (0.1-10):1, preferably (0.1-3):1, more preferably (0.2-2):1, and most preferably (0.3-1):1. In an even more preferred embodiment, the cobalt complex further contains a carbonyl coordinating group.

[0045] In a further preferred embodiment, the method of this application further includes a step of pretreating the hydromethoxygenation catalyst in the form of the cobalt complex solution in the presence of syngas containing CO and H2 before step 1). Preferably, the pretreatment conditions include: a temperature of 50-150°C, more preferably 75-130°C; a pressure of 0.1-12 MPa, more preferably 1-9 MPa, and more preferably 3-8 MPa; and a pretreatment time of 0.1-10 h, more preferably 1-3 h. In this preferred embodiment, the pretreatment step is beneficial to the formation of active units in the hydromethoxygenation catalyst, reduces catalyst decomposition, improves the activity and stability of the catalyst, and extends the catalyst's lifespan.

[0046] In a particularly preferred embodiment, the cobalt complex solution is obtained by reacting a cobalt-containing raw material with an organic phosphorus-containing coordination compound in the presence of an organic solvent. The cobalt-containing raw material is selected from cobalt salts, cobalt oxides, or combinations thereof, preferably from cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt acetopropionate, cobalt formate, dicobalt octacarbonyl, cobalt naphthenate, or combinations thereof. The organic phosphorus-containing coordination compound is as defined above. Preferably, the organic phosphorus-containing coordination compound is a compound containing phosphorus and a group bonded to phosphorus selected from hydrocarbon groups, hydroxyl groups, heterocyclic groups, or combinations thereof, more preferably a compound having the general formula PR3, wherein each group R is independently selected from hydrocarbon groups, hydroxyl groups, and heterocyclic groups, preferably independently selected from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, and aryloxy groups. Particularly preferably, the organophosphorus-containing coordinating compound is selected from phosphites, triarylphosphines, trialkylphosphines, alkylarylphosphines, or combinations thereof, such as triphenylphosphine, tributylphosphine, tritert-butylphosphine, tricyclohexylphosphine, dibutyldiphenylphosphine, ditert-butylneoptiylphosphine, trioctylphosphine, or combinations thereof. Preferably, the contact reaction conditions include: a temperature of 80-180°C, preferably 100-150°C; a pressure of 0.1-6 MPa, preferably 1-4 MPa; and a time of 0.5-24 h, preferably 1-15 h. More preferably, the contact reaction is carried out in the presence of CO, particularly in the presence of syngas containing CO and H₂.

[0047] According to this application, the organic compound with carbon-carbon double bonds used as a raw material for hydromethionization can be any organic compound having at least one carbon-carbon double bond in its carbon chain. The carbon-carbon double bond can be located at the end or in the middle of the carbon chain, and the organic compound can have hydroxyl groups, aromatic rings, etc. In a preferred embodiment, the organic compound with carbon-carbon double bonds is a hydrocarbon compound, such as an olefin. In a further preferred embodiment, the organic compound with carbon-carbon double bonds is an olefin having 3-60 carbon atoms, more preferably an olefin having 4-30 carbon atoms, even more preferably an olefin having 6-20 carbon atoms, and particularly preferably an olefin having 8-12 carbon atoms. The olefin can be a straight-chain olefin, a branched-chain olefin, a cycloolefin, or a mixed olefin containing any two or three of these, and the branched-chain olefin can have one or more branches. Most preferably, the olefin is a C8 olefin, such as an olefin selected from 1-octene and its various isomers, such as 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, 3,4,4-trimethyl-2-pentene, 2,3,3-trimethyl-1-pentene, 5,5-dimethyl-2-hexene, 3,5-dimethyl-2-hexene, 2,4-dimethyl-2-hexene, 2,3-dimethyl-3-hexene, and 3,4-dimethyl-2-hexene. Generally, trimethyl multi-branched olefins are more difficult to hydromethionize than olefins with fewer branches due to greater steric hindrance.

[0048] In a particularly preferred embodiment, step 1) of the method of this application includes: in the presence of the cobalt complex solution and at the first reaction temperature, contacting the C8 olefin with the synthesis gas to carry out a hydromethionization reaction to obtain a reaction material containing the oxygen-containing organic compound and the heavy material.

[0049] In a preferred embodiment, in step 1) of the method of this application, the ratio of the transition metal complex solution used as the hydromethionization catalyst to the organic compound having carbon-carbon double bonds by mass is (0.1-10):1, preferably (2-5):1.

[0050] In a preferred embodiment, the molar ratio of carbon monoxide to hydrogen in the syngas containing CO and H2 used in each step of the method of this application is independently 10:1 to 1:10, preferably 4:1 to 1:4, more preferably 3:1 to 1:3, for example 3:1 to 1:1, or 1:2 to 1:3. In each step, such as steps 1) and 2), the ratio of CO to H2 in the syngas used can be the same or different. This allows for convenient adjustment of the ratio between organic compounds with carbon-carbon double bonds and CO and H2 in each step to the optimal level, which is beneficial for achieving higher conversion rates and better selectivity.

[0051] The inventors of this application unexpectedly discovered that using a syngas with a high carbon monoxide to hydrogen molar ratio, such as a CO / H₂ molar ratio of 3:1 to 1:1, in step 1) can increase the aldehyde content in the reaction product of step 1), even though the amount of carbon monoxide and hydrogen in the syngas is still in significant excess for the reaction in step 1). Therefore, this implementation method is advantageous when aldehyde is the target product because the aldehyde product can be separated from the reaction product of step 1) after the reaction in step 1), thereby increasing the yield of the target aldehyde product.

[0052] Furthermore, the inventors of this application unexpectedly discovered that when some of the raw material organic compounds remain in the reaction product of step 1), the aldehyde content in the product is relatively high; while when the conversion rate of the raw material organic compounds is high or completely converted, the aldehyde content in the product is significantly reduced. Therefore, by controlling the raw material conversion rate of step 1) to <100%, and particularly controlling the raw material conversion rate of step 1) to <95%, and after the reaction in step 1), separating the unreacted raw material organic compounds from the reaction product of step 1) and recycling them back to step 1) for further reaction, the aldehyde yield of the reaction in step 1) can be improved.

[0053] In this application, there are no particular limitations on the reactors used for the reactions in steps 1) and 2), as long as the reactions can proceed and the temperature can be freely controlled. In a preferred embodiment, the reactions in steps 1) and 2) are carried out in the same or different tubular reactors. More preferably, the method is carried out continuously, and the reactions in steps 1) and 2) are carried out in different tubular reactors or in different regions of the same tubular reactor. During the reaction, the reactants (such as olefins, syngas, and catalyst solution) may flow into the tubular reactor from the bottom and the reaction products may flow out from the top; alternatively, the reactants may flow into the tubular reactor from the top and the reaction products may flow out from the bottom.

[0054] In some preferred embodiments, the reaction in step 2) is carried out with the addition of water.

[0055] In some other preferred embodiments, the reaction in step 2) is carried out without the addition of water.

[0056] In some specific embodiments, the method of this application further includes, before step 2), separating the reactants obtained in step 1) to separate the oxygen-containing organic compounds such as aldehydes, and then allowing the separated residues to continue reacting in step 2).

[0057] In a preferred embodiment, the method of this application further includes the following after step 2):

[0058] 3) Separate the reaction product obtained in step 2) to obtain a light component containing the oxygen-containing organic compound and a heavy component containing the hydromethionization catalyst and optionally, residual heavy matter; and

[0059] 4) Return at least a portion of the recombinant components obtained in step 3) to step 1) for further reaction.

[0060] According to this application, after the reaction in step 2) is completed, some organic oxygen-containing compound products (such as alcohols and aldehydes), by-product alkanes, and unreacted raw organic compounds can be separated (e.g., by distillation) from the crude reaction product. The remaining material containing the catalyst is recycled to step 1) for further reaction. Alternatively, the remaining material containing the catalyst can be recycled to a pretreatment step, pretreated, and then returned to step 1) for further reaction.

[0061] In a preferred embodiment, in step 4), the recycled heavy component contains 0.1-99.9 wt%, preferably 3-70 wt%, more preferably 3-30 wt% of the heavy material by mass.

[0062] In some preferred embodiments, the method of this application may further include hydrogenating the isolated oxygen-containing organic compound product to obtain an alcohol in high yield.

[0063] In some preferred embodiments, the method of this application is carried out in a continuous manner and includes the following steps:

[0064] i) In the presence of the hydromethionization catalyst and at a first reaction temperature, C8 olefins are subjected to a hydromethionization reaction in a syngas atmosphere containing CO and H2 to obtain a first stream containing C9 aldehydes and C9 alcohols, the first stream also containing heavy matter;

[0065] ii) Under a syngas atmosphere containing CO and H2 and at a second reaction temperature, the first stream obtained in step i) is allowed to continue reacting, causing the heavy components to decompose and yielding a second stream with a reduced heavy component content;

[0066] iii) The second stream is separated to obtain a light component and a heavy component, wherein the light component contains C9 alcohols, C9 aldehydes, and C8 alkanes, and the heavy component contains the hydromethionization catalyst and optionally residual heavy matter; and

[0067] iv) Recycle at least a portion of the recombinant components back to step i) for the hydromethionization reaction;

[0068] Preferably, in step iii), the separation can be performed by first performing gas-liquid separation and then by distillation separation.

[0069] In a further preferred embodiment, the gas-liquid separation is carried out in a gas-liquid separation tank under the condition of cooling without pressure reduction, and the gas-liquid separation temperature is 0-100℃, preferably 20-80℃, and more preferably 20-40℃.

[0070] In a further preferred embodiment, the gaseous stream obtained after gas-liquid separation is mainly syngas. After condensation and / or absorption, the remaining syngas can be recycled to the inlet of the pretreatment reactor and / or the reactor used in step i) for reuse.

[0071] The liquid phase stream after gas-liquid separation can be distilled and separated by a distillation apparatus. The top product is a mixed product containing C9 alcohol, C8 alkane and C9 aldehyde, and the bottom product contains a heavy component containing the hydromethionization catalyst and a solvent.

[0072] In a preferred embodiment, the amount of the recombinant component recycled back to step i) in step iv) is 0.1-90 wt%, preferably 0.1-40 wt%, and more preferably 0.1-20 wt%, of the total recombinant component obtained in step iii). More preferably, the recombinant component recycled back to step i) contains a certain amount of the heavy material, for example, 0.1-99.9 wt%, preferably 3-70 wt%, and more preferably 3-30 wt% of the heavy material based on the mass of the recycled recombinant component. The inventors of this application have unexpectedly discovered that including a certain amount of heavy material in the recycled recombinant component can improve the solubility of the catalyst, thereby facilitating a reduction in the reaction temperature and alkane selectivity in step i).

[0073] In a preferred embodiment, when the recombinant component is returned to the reactor and / or pretreatment reactor inlet used in step i) to participate in the hydromethionization reaction, a small amount of fresh catalyst may be added as needed.

[0074] In a particularly preferred embodiment, the method of this application is carried out in a continuous manner and includes the following steps:

[0075] A) A cobalt complex catalyst solution containing an organic phosphorus-containing ligand is fed into a first tubular reactor along with a C8 olefin, and a hydromethionization reaction is carried out at a first reaction temperature and under a syngas atmosphere;

[0076] B) The reaction product obtained in step A) is fed into a second tubular reactor for further reaction at a second reaction temperature and under a syngas atmosphere;

[0077] C) The reaction product obtained in step B) is separated to obtain a light component and a heavy component, wherein the light component comprises C9 alcohols, C9 aldehydes, and C8 alkanes, and the heavy component comprises the cobalt complex catalyst; and

[0078] D) Return at least a portion of the recombinant components obtained in step C) to the inlet of the first tubular reactor for recycling.

[0079] In the particularly preferred embodiment described above, in step A), the C8 olefin is first converted into C8 alkanes, C9 aldehydes, C9 alcohols, and heavy compounds at a lower reaction temperature; then, in step B), the heavy compounds are converted into C9 alcohols at a higher reaction temperature. Analysis shows that the hydromethionization reaction in step A) yields a reaction product containing heavy compounds, while the reaction in step B) unexpectedly causes the heavy compounds to decompose back into C9 alcohols and other products, with virtually no C8 alkanes produced.

[0080] More preferably, a portion of the heavy components obtained in step C) is discharged from the reaction system. More preferably, this portion of the heavy components is sent to a downstream reaction unit before being discharged from the system, where syngas is introduced but the raw material organic compounds are not introduced. Post-treatment is carried out under higher temperature conditions, and the residual heavy matter therein will decompose into products such as C9 alcohols. This not only further increases the yield of the target product, but also significantly reduces the amount of discharged material, thereby significantly reducing waste liquid discharge and alleviating the environmental problems of the hydromethionization process.

[0081] The method for preparing oxygen-containing organic compounds by hydromethionization in this application has one or more of the following advantages:

[0082] 1. Significantly reduces alkane selectivity and increases alcohol selectivity, thereby significantly improving the economic efficiency of the process;

[0083] 2. By decomposing heavy materials back into products such as alcohols in the second step of the reaction, the selectivity of alcohols can be improved, the amount of waste material discharged can be significantly reduced, and the amount of waste liquid can be reduced, which is beneficial to environmental protection and has industrialization prospects.

[0084] 3. It is applicable to a wide range of raw materials, especially suitable for the hydromethionization of multi-branched olefins with large steric hindrance; the reaction pressure is low, and the equipment investment and processing costs are significantly reduced.

[0085] 4. In the first step of the hydromethionization reaction, a cobalt catalyst, which is cheaper than a rhodium catalyst, can be used, and the reaction temperature in the first step is significantly reduced, which is beneficial to the stability of the cobalt catalyst;

[0086] 5. In the preferred embodiment, the catalyst pretreatment process can reduce the decomposition of cobalt complex catalysts, which is beneficial to the formation of active units in cobalt complex catalysts, improves the activity and stability of the catalyst, and extends the catalyst's service life;

[0087] 6. In some preferred embodiments, extending the reaction time of the second step can reduce the aldehyde content in the reaction product of the second step to <0.1 wt%, which is advantageous when the target product is an alcohol, because the subsequent hydrogenation step of converting the aldehyde into an alcohol can be omitted.

[0088] 7. By changing the composition of the syngas used in the first step of the hydromethionization reaction, the ratio of alcohols and aldehydes in the products of the first step of the reaction can be adjusted, thereby producing more aldehydes as needed, which is beneficial to product diversification.

[0089] Example

[0090] The present application will be further illustrated by the following examples, but the present application is not limited thereto.

[0091] In the following examples and comparative examples, unless otherwise specified, all raw materials used are commercially available products with industrial purity.

[0092] In Examples 1-5 and Comparative Examples 1-2 below, the olefin feedstock used was a commercially available C8 olefin with the following composition: 75.1 wt% of 2,4,4-trimethyl-1-pentene, 21.2 wt% of 2,4,4-trimethyl-2-pentene, and the remainder being multi-branched olefins; the syngas used had a CO / H2 molar ratio of 1:2.

[0093] In the following examples and comparative examples, the formula for calculating the raw material conversion rate is as follows:

[0094] The conversion rate of the raw materials is calculated as follows: [1 - (total mass of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene in the reaction products) / (total mass of 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene in the raw materials)] × 100%.

[0095] Catalyst Preparation Example 1

[0096] In a reactor, cobalt naphthenate and triphenylphosphine were dissolved in isononol, with the amount of cobalt being 0.13 wt% and phosphorus being 0.07 wt% in the resulting solution. The air was replaced with syngas, and the pressure was increased to 1.7 MPa. The reaction was carried out at 140°C for 9 h with stirring at 400 rpm to obtain a cobalt-phosphine complex solution, denoted as catalyst solution A1, the composition of which is shown in Table 1.

[0097] Catalyst Preparation Example 2

[0098] In a reactor, cobalt naphthenate and triphenylphosphine were dissolved in isononol, with the amount of cobalt added so that the resulting solution contained 0.1 wt% cobalt and 0.06 wt% phosphorus. The air was replaced with syngas, and the pressure was increased to 1.8 MPa. The mixture was stirred at 400 rpm and reacted at 140 °C for 9 h to obtain a cobalt-phosphine complex solution, denoted as catalyst solution A2. Its composition is shown in Table 1.

[0099] Catalyst Preparation Example 3

[0100] In a reactor, cobalt naphthenate and triphenylphosphine were dissolved in isononol, with the amount of cobalt being 0.077 wt% and phosphorus being 0.069 wt% in the resulting solution. The air was replaced with syngas, and the pressure was increased to 2 MPa. The mixture was stirred at 400 rpm and reacted at 140°C for 9 h to obtain a cobalt-phosphine complex solution, denoted as catalyst solution A3. Its composition is shown in Table 1.

[0101] Catalyst Preparation Example 4

[0102] In a reactor, cobalt naphthenate and triphenylphosphine were dissolved in isononol, with the amount of cobalt being 0.11 wt% and phosphorus being 0.07 wt% in the resulting solution. The air was replaced with syngas, and the pressure was increased to 2 MPa. The reaction was carried out at 140°C for 9 h with stirring at 400 rpm to obtain a cobalt-phosphine catalyst solution, denoted as catalyst solution A4. Its composition is shown in Table 1.

[0103] Catalyst Preparation Example 5

[0104] In a reactor, cobalt naphthenate and triphenylphosphine were dissolved in isononol, with the amount of cobalt and phosphorus in the resulting solution being 0.1 wt%. The air was replaced with syngas and the pressure was increased to 3 MPa. The reaction was carried out at 110°C for 20 h with stirring at 400 rpm to obtain a cobalt-phosphine complex solution, denoted as catalyst solution A5, the composition of which is shown in Table 1.

[0105] Table 1 Composition of catalyst solutions A1 to A4 Wrong Combination solvent cobalt phosphorus A1 0.13 wt% 0.07 wt% Isononol A2 0.10 wt% 0.06 wt% Isononol A3 0.077 wt% 0.069 wt% Isononol A4 0.11 wt% 0.07 wt% Isononol A5 0.1 wt% 0.1 wt% Isononol

[0106] Example 1

[0107] Catalyst solution A1 (recycled during the reaction) and syngas were added to a pretreatment reactor at a temperature of 125℃ and a pressure of 8 MPa for 0.5 h. The pretreated catalyst solution A1 and C8 olefins were then introduced into a first tubular reactor at a ratio of 83 g: 30 g. The first tubular reactor was maintained at a temperature of 120℃ and a pressure of 8 MPa, and syngas was introduced during the reaction for 15 h. The products were then analyzed by chromatography, and the results are shown in Table 2-1.

[0108] The effluent from the first tubular reactor entered the second tubular reactor, which was operated at a temperature of 153-155℃ and a pressure of 8 MPa, with syngas introduced and reacted for 4 hours. The products were then subjected to chromatographic analysis, and the results are shown in Table 2-1.

[0109] Table 2-1 Reaction results of Example 1 2,2,4-Trimethylpentane Heavy matter Isononaldehyde Isononol raw material Conversion rate Step 1) Product 2.5 wt% 47.4 wt% 11.3 wt% 35.7 wt% 92.8 wt% Step 2) Product 2.6 wt% 18.9 wt% 9 wt% 68.8 wt% 99.7 wt%

[0110] As shown in Table 2-1, compared with the product of step 1), the heavy matter content in the product of step 2) is reduced, and the reduced heavy matter is basically converted into isononanol, while the amount of the byproduct 2,2,4-trimethylpentane remains basically unchanged. Furthermore, through step 2), the raw material conversion rate is increased from 92.8 wt% to 99.7 wt%, which basically achieves complete conversion of the raw material.

[0111] Compare with Example 1

[0112] The experiment was conducted according to Example 1, except that the temperature of the second tubular reactor was 120°C, the pressure was 8 MPa, and syngas was introduced for 4 h. After the reaction, the product was subjected to chromatographic analysis. The results showed that compared with the product of step 1), the content of heavy matter in the product of step 2) increased by 1 wt%, while the content of isononol was basically the same as that in the product of step 1). This indicates that when reacting in the second tubular reactor at a lower temperature, the heavy matter cannot be well converted into isononol, and its content actually increases.

[0113] Example 2

[0114] Catalyst solution A2 (recycled during the reaction) and syngas were added to a pretreatment reactor at a temperature of 150℃ and a pressure of 8 MPa for 0.5 h. The pretreated catalyst solution A2 and C8 olefins were then introduced into a first tubular reactor at a ratio of 83 g: 30 g. The first tubular reactor was maintained at a temperature of 150℃ and a pressure of 8 MPa, and syngas was added for 12 h of reaction. The products were then analyzed by chromatography, and the results are shown in Table 2-2.

[0115] The effluent from the first tubular reactor entered the second tubular reactor, which was operated at 180℃ and 8 MPa, with syngas introduced and reacted for 2 hours. The products were then subjected to chromatographic analysis, and the results are shown in Table 2-2.

[0116] Table 2-2 Reaction results of Example 2 2,2,4-Trimethylpentane Heavy matter Isononaldehyde Isononol raw material Conversion rate Step 1) Product 3.2 wt% 20.7 wt% 3.4 wt% 69.3 wt% 91.6 wt% Step 2) Product 3.3 wt% 8 wt% 0.5 wt% 87.1 wt% 99.7 wt%

[0117] As shown in Table 2-2, compared with the product of step 1), the heavy matter content in the product of step 2) is reduced, and the reduced heavy matter is basically converted into isononanol, while the amount of the byproduct 2,2,4-trimethylpentane remains basically unchanged. Furthermore, through step 2), the raw material conversion rate is increased from 91.6 wt% to 99.7 wt%, which basically achieves complete conversion of the raw material.

[0118] Compare with Example 2

[0119] The experiment was conducted according to Example 2, the difference being that the temperature of both the first and second tubular reactors was 180°C, and the products were analyzed by chromatography after the reaction. The results showed that the content of the byproduct 2,2,4-trimethylpentane in the final product of Example 2 was as high as 7 wt%, and the content of 2,2,4-trimethylpentane was significantly increased.

[0120] Example 3

[0121] Catalyst solution A3 (recycled during the reaction) and syngas were added to the pretreatment reactor at a temperature of 130℃ and a pressure of 8 MPa for 0.5 h. The pretreated catalyst solution A3 and C8 olefins were then introduced into the first tubular reactor at a ratio of 330 g: 30 g. The first tubular reactor was maintained at a temperature of 130℃ and a pressure of 8 MPa, and syngas was introduced for 8 h of reaction. The products were then analyzed by chromatography, and the results are shown in Table 2-4.

[0122] The effluent from the first tubular reactor entered the second tubular reactor, which was operated at 155℃ and 8 MPa, with syngas introduced and reacted for 5 h. The products were then subjected to chromatographic analysis, and the results are shown in Table 2-3.

[0123] Table 2-3 Reaction results of Example 3 2,2,4-Trimethylpentane Heavy matter Isononaldehyde Isononol raw material Conversion rate Step 1) Product 1.1 wt% 59.6 wt% 5.9 wt% 31.3 wt% 88.3 wt% Step 2) Product 1.4 wt% 49.3 wt% 0.7 wt% 47.6 wt% 98.9 wt%

[0124] As shown in Table 2-3, compared with the product of step 1), the heavy matter content in the product of step 2) is reduced, and the reduced heavy matter is basically converted into isononanol, while the amount of byproduct 2,2,4-trimethylpentane remains basically unchanged. Furthermore, through step 2), the raw material conversion rate is increased from 88.3 wt% to 98.9 wt%, which basically achieves complete conversion of the raw material.

[0125] Example 4

[0126] The experiment was conducted according to Example 1, except that catalyst solution A4 was used instead of catalyst solution A1. The reaction time in the first tubular reactor was 23 h, and the temperature in the second tubular reactor was 150 °C, the pressure was 8 MPa, 2.5 wt% water was added, and syngas was introduced for 5 h. The products were analyzed by chromatography after the reaction, and the results are shown in Tables 2-4.

[0127] Table 2-4 Reaction results of Example 4 2,2,4-Trimethylpentane Heavy matter Isononaldehyde Isononol raw material Conversion rate Step 1) Product 2.0 wt% 16.7 wt% 7.9 wt% 70.9 wt% 91.8 wt% Step 2) Product 2.2 wt% 14.9 wt% 1.3 wt% 80.9 wt% 99.9 wt%

[0128] As shown in Table 2-4, compared with the product of step 1), the heavy matter content in the product of step 2) is reduced, and the reduced heavy matter is basically converted into isononanol, while the amount of the byproduct 2,2,4-trimethylpentane remains basically unchanged. Furthermore, through step 2), the raw material conversion rate is increased from 91.8 wt% to 99.9 wt%, which basically achieves complete conversion of the raw material.

[0129] Example 5

[0130] The experiment was conducted according to Example 2, except that the reaction temperature in the higher reaction temperature section of the second tubular reaction zone was 180°C, the pressure was 8 MPa, and the reaction time was 2 h. Then, at a reaction temperature of 180°C and a pressure of 8 MPa, 3 wt% water was added and syngas was introduced for another 2 h. The products were then analyzed by chromatography, and the results are shown in Tables 2-5.

[0131] Table 2-5 Reaction results of Example 5 2,2,4-Trimethylpentane Heavy matter Isononaldehyde Isononol raw material Conversion rate Step 1) Product 3.2 wt% 20.7 wt% 3.4 wt% 69.3 wt% 91.6 wt% Step 2) Product 2.7 wt% 5.3 wt% 0.04 wt% 91 wt% 99.9 wt%

[0132] As shown in Table 2-5, compared with the product of step 1), the product of step 2) has a lower content of heavy matter, and the reduced heavy matter is almost entirely converted into isononanol. The content of the byproduct 2,2,4-trimethylpentane is slightly reduced, while isononanol can be reduced to <0.1 wt%. This is advantageous when isononanol is the target product because the subsequent hydrogenation step to convert isononanol to isononanol is unnecessary (the aldehyde content in the isononanol standard must be <0.1 wt%). Furthermore, through step 2), the feed conversion rate increases from 91.6 wt% to 99.9 wt%, essentially achieving complete feed conversion.

[0133] In Examples 6-8 below, the olefin feedstock used is a commercially available C8 olefin with the following composition: 64.7 wt% of 2,4,4-trimethyl-1-pentene, 18.5 wt% of 2,4,4-trimethyl-2-pentene, and the remainder is mainly multi-branched olefins.

[0134] Example 6

[0135] Catalyst solution A5 (recycled during the reaction) and syngas (CO / H₂ molar ratio of 1:2) were added to the pretreatment reactor. The pretreatment reactor was maintained at 100℃ and 8 MPa for 1 h. The pretreated catalyst solution A5 and C8 olefins were then introduced into the first tubular reactor at a ratio of 110 g: 73.4 g. The first tubular reactor was maintained at 130℃ and 8 MPa, and syngas (CO / H₂ molar ratio of 1:2) was introduced for 15 h. The products were then analyzed by chromatography, and the results are shown in Table 2-7.

[0136] The effluent from the first tubular reactor entered the second tubular reactor, which was operated at 180℃ and 8 MPa, with syngas (CO / H₂ molar ratio of 1:2) introduced and reacted for 7 h. The products were then analyzed by chromatography, and the results are shown in Table 2-6.

[0137] Table 2-6 Reaction results of Example 6 2,2,4-Trimethylpentane Heavy matter Isononaldehyde Isononol raw material Conversion rate Step 1) Product 5.7 wt% 21.6 wt% 10.2 wt% 45.3 wt% 98.2 wt% Step 2) Product 5.8 wt% 2.6 wt% 0.15 wt% 74.2 wt% 100 wt%

[0138] As shown in Table 2-6, compared with the product of step 1), the heavy matter content in the product of step 2) is reduced, and the reduced heavy matter is basically converted into isononanol, while the amount of byproduct 2,2,4-trimethylpentane remains basically unchanged. Furthermore, through step 2), the raw material conversion rate is increased from 98.2 wt% to 100 wt%, achieving complete conversion of the raw material.

[0139] Meanwhile, extending the reaction time of step 2) to 10 h can reduce the isononal content in the product to 0 wt%, while other components remain largely unchanged.

[0140] Example 7

[0141] The experiment was conducted according to Example 6, except that the CO / H₂ molar ratio of the syngas used in each step was 1:1, the temperature of the second tubular reactor was 180°C, the pressure was 8 MPa, 1.5 wt% water was added, and syngas was introduced for 7 h. The products were then analyzed by chromatography, and the results are shown in Tables 2-7.

[0142] Table 2-7 Reaction results of Example 7 2,2,4-Trimethylpentane Heavy matter Isononaldehyde Isononol raw material Conversion rate Step 1) Product 3.7 wt% 22.6 wt% 20.7 wt% 33.5 wt% 92.4 wt% Step 2) Product 3.3 wt% 3 wt% 0.1 wt% 77 wt% 100 wt%

[0143] As shown in Table 2-7, compared with the product of step 1), the heavy matter content in the product of step 2) is reduced, and the reduced heavy matter is basically converted into isononanol, while the amount of the byproduct 2,2,4-trimethylpentane is slightly reduced. Furthermore, by increasing the feed conversion rate from 92.4 wt% to 100 wt% in step 2), the isononanol content can be reduced to 0.1 wt%, thus eliminating the need for the subsequent isononanol hydrogenation step and achieving complete feed conversion.

[0144] Meanwhile, extending the reaction time of step 2) to 10 h can reduce the isononal content in the product to 0 wt%, while other components remain largely unchanged.

[0145] Example 8

[0146] The experiment was conducted according to Example 6, except that the CO / H₂ molar ratio of the syngas used in each step was 2:1, and the temperature of the second tubular reactor was 180°C, the pressure was 8 MPa, 1.5 wt% water was added, and syngas was introduced for 7 h. The products were then analyzed by chromatography, and the results are shown in Tables 2-8.

[0147] Table 2-8 Reaction results of Example 8 2,2,4-Trimethylpentane Heavy matter Isononaldehyde Isononol raw material Conversion rate Step 1) Product 4.1 wt% 27.6 wt% 21.0 wt% 29.5 wt% 96.6 wt% Step 2) Product 3.8 wt% 4.5 wt% 2.5 wt% 72.5 wt% 100 wt%

[0148] As shown in Table 2-8, compared with the product of step 1), the heavy matter content in the product of step 2) is reduced, and the reduced heavy matter is basically converted into isononanol, while the amount of the byproduct 2,2,4-trimethylpentane is slightly reduced. Furthermore, through step 2), the raw material conversion rate is increased from 96.6 wt% to 100 wt%, achieving complete conversion of the raw material.

[0149] Comparing the data in Tables 2-6 to 2-8, it can be found that, compared with Example 6, which uses syngas with a normal CO / H2 molar ratio (i.e., CO / H2 = 1:2), Examples 7-8, which use syngas with a higher CO / H2 molar ratio than the normal stoichiometric ratio, still contain a higher content of isononanal and a lower alkane content in the product of step 1), even with a feed conversion rate >95% in step 1) (as in Example 8). This is unusual because the reaction in step 1) is carried out in a syngas atmosphere, resulting in a significant excess of carbon monoxide and hydrogen compared to the alkene reaction requirements. When isononanal is the target product, using a higher CO / H2 molar ratio in the syngas is more advantageous, allowing for the separation of the aldehyde product from the reaction product of step 1) before step 2), thereby increasing the yield of isononanal.

[0150] The experimental results above show that the two-step reaction method of this application can significantly reduce the alkane selectivity in the preparation of oxygen-containing organic compounds by olefin hydromethionization, while improving the alcohol selectivity.

[0151] The preferred embodiments of this application have been described in detail above. However, this application is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this application, various simple modifications can be made to the technical solution of this application, and these simple modifications all fall within the protection scope of this application.

[0152] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way without contradiction. In order to avoid unnecessary repetition, this application will not describe the various possible combinations separately.

[0153] Furthermore, various different implementations of this application can be combined in any way, as long as they do not violate the spirit of this application, they should also be regarded as the content disclosed in this application.

[0154] none

Claims

1. A method for preparing an oxygen-containing organic compound by hydromethionization, comprising the following steps: 1) in the presence of a hydromethionization catalyst and at a first reaction temperature, contacting an organic compound having 2-60 carbon atoms and at least one carbon-carbon double bond with a syngas containing CO and H2 to perform a hydromethionization reaction, obtaining a reactant containing the oxygen-containing organic compound and a heavy substance, wherein the oxygen-containing organic compound is an alcohol, aldehyde, or a combination thereof that has one more carbon atom than the organic compound having a carbon-carbon double bond, and the first reaction temperature is 60°C to less than 130°C; and 2) in the presence of a syngas containing CO and H2 and at a second reaction temperature, continuing to react the reactant obtained in step 1) to decompose the heavy substance therein, obtaining a reaction product with a reduced content of the heavy substance and an increased content of the oxygen-containing organic compound, wherein the second reaction temperature is 140-200°C, and the second reaction temperature is 20-100°C higher than the first reaction temperature.

2. The method as described in request item 1, wherein: The reaction conditions for step 1) include: a reaction temperature of 60°C to less than 130°C; a reaction pressure of 1-12 MPa; and a reaction time of 1-60 h; and the reaction conditions for step 2) include: a reaction temperature of 140-200°C; a reaction pressure of 1-12 MPa; and a reaction time of 1-40 h.

3. The method of claim 1, wherein the hydromethoxygenation catalyst is a transition metal complex catalyst, the transition metal complex comprising a carbonyl ligand, an organic phosphorus-containing ligand, or a combination thereof, wherein the organic phosphorus-containing ligand is a ligand comprising phosphorus and a group selected from hydrocarbon groups, alkyl groups, heterocyclic groups, or combinations thereof bonded to phosphorus.

4. The method of claim 3, wherein the hydromethionization catalyst is used in the form of a solution of the transition metal complex in an organic solvent, wherein the mass concentration of the transition metal in the solution is 0.01-3%, and the organic solvent is selected from alkanes, aromatics, alcohols, ethers, aldehydes, ketones, nitriles, esters, or combinations thereof.

5. The method of claim 4, wherein the transition metal complex is a cobalt complex containing the organic phosphorus-containing ligand, and the mass concentration of cobalt in the cobalt complex solution is 0.01-3%.

6. The method of claim 5, wherein the cobalt complex solution is obtained by reacting a cobalt-containing raw material with an organophosphorus-containing coordination compound in the presence of an organic solvent, wherein the cobalt-containing raw material is selected from cobalt salts, cobalt oxides, or combinations thereof; and the organophosphorus-containing coordination compound is a compound comprising phosphorus and a group selected from hydrocarbon groups, hydroxyl groups, heterocyclic groups, or combinations thereof bonded to phosphorus. The conditions for the contact reaction include: temperature of 80-180℃; pressure of 0.1-6 MPa; and time of 0.5-24 h.

7. The method of claim 5, wherein the method further comprises a step of pretreating the hydromethoxygenation catalyst in the presence of syngas containing CO and H2 prior to step 1), the pretreating conditions including: The temperature is 50-150℃; The pressure is 0.1-12 MPa; The pretreatment time is 0.1-10 h.

8. The method of any one of claims 1-7, wherein the organic compound having a carbon-carbon double bond is an olefin having 3-60 carbon atoms.

9. The method as described in claim 6, wherein step 1) comprises: In the presence of the cobalt complex solution and at the first reaction temperature, the C8 olefin is contacted with the syngas to undergo a hydromethionization reaction, yielding a reactant containing the oxygen-containing organic compound and a heavy substance, wherein the C8 olefin is selected from 1-octene and its various isomers.

10. The method of any one of claims 4-7 and 9, wherein, by mass, the ratio of the transition metal complex solution used as the hydromethionization catalyst in step 1) to the organic compound having a carbon-carbon double bond is (0.1-10):

1.

11. The method of claim 1, wherein the molar ratio of carbon monoxide to hydrogen in the synthesis gas containing CO and H2 used in each step is independently from 10:1 to 1:

10.

12. The method of claim 1, wherein the reactions in step 1) and step 2) are carried out in the same or different tubular reactors.

13. The method of claim 1, wherein the method further comprises, prior to step 2): The reactants obtained in step 1) are separated to extract the oxygen-containing organic compounds, and the residue obtained after separation is then allowed to continue reacting in step 2).

14. The method of claim 1, wherein the method further comprises, after step 2): 3) Separate the reaction product obtained in step 2) to obtain a light component containing the oxygen-containing organic compound and a heavy component containing the hydromethionization catalyst and optional residual heavy matter; and 4) return at least a portion of the heavy component obtained in step 3) to step 1) for further reaction, wherein the recycled heavy component contains 0.1-99.9 wt% of the heavy matter by mass.

15. The method of request 1, wherein the reaction in step 2) is carried out with the addition of water.

16. The method as described in claim 1, wherein the reaction conditions of step 1) include: The reaction temperature is 100-145℃; The reaction pressure is 2-10 MPa; The reaction time is 2-25 hours. The reaction conditions for step 2) include: a reaction temperature of 170-200℃; a reaction pressure of 2-10 MPa; and a reaction time of 2-25 h; both steps 1) and 2) are carried out in a syngas atmosphere.

17. The method of claim 3, wherein the transition metal in the transition metal complex is selected from rhodium (Rh), cobalt (Co), iridium (Ir), ruthenium (Ru), or combinations thereof; and the organic phosphorus-containing ligand is a ligand having the general formula PR3, wherein each group R is independently selected from hydrocarbon groups, hydroxyl groups, and heterocyclic groups.

18. The method of claim 17, wherein each group R is independently derived from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, and aryloxy groups.