Method for preparing iso-tridecanol from Fischer-Tropsch olefin
By using the synergistic catalysis of the Fischer-Tropsch C6 fraction with alkylaluminum and supported metals, combined with the hydroformylation reaction of cobalt catalyst and bisphosphine ligand, the problems of low reactivity and high energy consumption in the preparation of isotridecyl alcohol in the past have been solved, and the efficient preparation of isotridecyl alcohol has been achieved, which is suitable for industrial application.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-24
- Publication Date
- 2026-04-10
AI Technical Summary
In existing methods for preparing isomeric tridecyl alcohol, dodecene contains many branches, resulting in low reactivity. The hydroformylation reaction conditions are harsh, energy consumption is high, and economic efficiency is poor, leading to low selectivity and yield of the target product.
Polymerization was carried out by mixing alkyl aluminum and supported metal with the Fischer-Tropsch C6 fraction, followed by hydroformylation with a cobalt catalyst and bisphosphine ligand, and then hydrogenation of the aldehyde in the presence of a hydrogenation catalyst to prepare isomeric tridecanol.
It improves the conversion rate of isododecylene and the selectivity of isotridecylaldehyde, reduces the harshness of reaction conditions, enhances process stability, and increases the yield of isotridecyl alcohol, resulting in good economic benefits and suitability for large-scale industrial production.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of organic alcohol preparation technology, and specifically to a method for preparing isomeric tridecanol from Fischer-Tropsch olefins. Background Technology
[0002] Isotridecanol, a key raw material for the synthesis of isomeric alcohol ethers, possesses excellent water solubility and dispersion properties, along with outstanding wetting, penetrating, and emulsifying capabilities. These characteristics enable its widespread application in numerous fields, including surfactants, antioxidants, UV-curable materials, coatings, and lubricants, playing an irreplaceable role, particularly in the textile, paper, and pharmaceutical industries. However, my country, as a major consumer of isotridecanol, currently faces a severe supply situation. Due to limitations in resources and technology, my country's reliance on imports for isotridecanol is relatively high. Therefore, developing an efficient isotridecanol preparation process has become a top priority to meet the urgent needs of industrial production.
[0003] In actual industrial production, isomeric tridecanol is mainly produced through butene trimerization or propylene tetramerization, followed by hydroformylation and hydrogenation. However, the dodecene generated during the polymerization process contains a large number of branched structures, which makes dodecene less reactive in the hydroformylation reaction. To promote the hydroformylation reaction, higher pressure and temperature conditions must be used. But under these conditions, side reactions increase significantly, leading to a substantial decrease in raw material utilization. Summary of the Invention
[0004] The purpose of this invention is to overcome the problems of existing methods for preparing isotridecyl alcohol, such as the dodecene in the reactants having many branches, low reactivity, harsh hydroformylation reaction conditions, high energy consumption, poor economy, numerous reaction byproducts, and low selectivity and yield of the target product. This invention provides a method for preparing isotridecyl alcohol from Fischer-Tropsch olefins. This method features readily available raw materials, high conversion rate, good selectivity, high yield of isotridecyl alcohol, mild reaction conditions, and strong process stability. Furthermore, the method is simple and convenient to operate, has good economic benefits, and highly meets the needs of large-scale industrial production, demonstrating significant economic value and broad industrial application prospects.
[0005] To achieve the above objectives, the present invention provides a method for preparing isomeric tridecanol from Fischer-Tropsch olefins, the method comprising the following steps:
[0006] (1) Mix the Fischer-Tropsch C6 fraction, alkyl aluminum and supported metal, and then pass hydrogen into the resulting mixture to carry out a polymerization reaction to obtain isomeric dodecene.
[0007] (2) Mix the isododecene, cobalt catalyst and bisphosphine ligand, and then introduce syngas into the resulting reaction mixture to carry out hydroformylation reaction to obtain isotridecaldehyde.
[0008] (3) In the presence of a hydrogenation catalyst, the isomeric tridecanal is mixed with hydrogen to carry out an aldehyde hydrogenation reaction;
[0009] The alkylaluminum is selected from at least one of triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum;
[0010] The metal element contained in the load metal is a transition metal element.
[0011] Preferably, the transition metal element is iron, zinc, cobalt, nickel, copper, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, molybdenum, or technetium.
[0012] Preferably, the loaded metal is at least one of a water-soluble metal halide, oxide, sulfate, and nitrate.
[0013] Preferably, in step (1), the weight ratio of the loaded metal to the Fischer-Tropsch C6 fraction is 1:10-10000.
[0014] Preferably, the molar ratio of the loaded metal to the alkyl aluminum is 1:1-100.
[0015] Preferably, in step (1), the Fischer-Tropsch C6 fraction contains 20-40% by weight of n-alkanes, 30-60% by weight of n-olefins, 10-25% by weight of isoolefins and 1-5% by weight of oxygen-containing compounds.
[0016] Preferably, in step (1), hydrogen gas is introduced to make the pressure of the reaction system 0.5-1.5 MPaG.
[0017] Preferably, the conditions for the polymerization reaction include: a temperature of 25-40°C and a time of 2-5 hours.
[0018] Preferably, in step (2), the content of the cobalt catalyst is 0.1-1.3% by weight, based on the total weight of the isododecene, the cobalt catalyst, and the bisphosphine ligand.
[0019] Preferably, the molar ratio of the bisphosphine ligand to the cobalt catalyst is 1:0.3-5.
[0020] Preferably, the cobalt catalyst is selected from at least one of cobalt chloride, cobalt sulfate, cobalt acetate, cobalt carbonate, cobalt nitrate, cobalt oxide, and octacarbonyldicobalt.
[0021] Preferably, the bisphosphine ligand is 6,6′-[(3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-diphenyl-2,2′-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxophosphatane) and / or 4,5-bis(diphenylphosphino)-9,9-dimethyloxanthracene.
[0022] Preferably, in step (2), the synthesis gas is introduced to make the initial pressure of the reaction system 1-15 MPaG.
[0023] Preferably, the volume ratio of H2 to CO in the synthesis gas is 0.9-3.5:1.
[0024] Preferably, in step (2), the conditions for the hydroformylation reaction include: a temperature of 85-220°C, a pressure of 1-15 MPaG, and a time of 2-10 h.
[0025] Preferably, in step (3), hydrogen gas is introduced to make the pressure of the reaction system 0.5-5 MPaG.
[0026] Preferably, the liquid hourly space velocity (LISH) of the isomeric tridecanal is 0.5-8 hr. -1 .
[0027] Preferably, the hydrogenation catalyst is selected from at least one of copper-zinc catalysts, nickel-based catalysts, and palladium-based catalysts.
[0028] Preferably, in step (3), the conditions for the aldehyde hydrogenation reaction include a temperature of 100-200℃.
[0029] The method described in this invention uses Fischer-Tropsch C6 fraction, which has a high olefin content, is readily available, and is inexpensive, as raw material. A polymerization reaction is carried out under the synergistic catalysis of alkyl aluminum and supported metals to achieve efficient conversion of the Fischer-Tropsch C6 fraction to isododecene, thereby increasing the yield of isododecene. Subsequently, the isododecene undergoes hydroformylation under the synergistic catalysis of a cobalt catalyst and bisphosphine ligands. This effectively suppresses the formation of byproducts, improves the selectivity of isotridecaldehyde, and achieves efficient conversion of isododecene to isotridecaldehyde, thereby increasing the yield of isotridecaldehyde and significantly improving the yield of isotridecyl alcohol in the subsequent aldehyde hydrogenation reaction. Furthermore, this method features mild reaction conditions, stronger process stability, simple and convenient operation, and good economic benefits, highly meeting the needs of large-scale industrial production and demonstrating significant economic value and broad industrial application prospects. Detailed Implementation
[0030] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.
[0031] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0032] The method for preparing isomeric tridecanol from Fischer-Tropsch olefins according to the present invention includes the following steps:
[0033] (1) Mix the Fischer-Tropsch C6 fraction, alkyl aluminum and supported metal, and then pass hydrogen into the resulting mixture to carry out a polymerization reaction to obtain isomeric dodecene.
[0034] (2) Mix the isododecene, cobalt catalyst and bisphosphine ligand, and then introduce syngas into the resulting reaction mixture to carry out hydroformylation reaction to obtain isotridecaldehyde.
[0035] (3) In the presence of a hydrogenation catalyst, the isomeric tridecanal is mixed with hydrogen to carry out an aldehyde hydrogenation reaction.
[0036] In the method described in this invention, the Fischer-Tropsch C6 fraction used is derived from oil-washed naphtha Fischer-Tropsch synthesis, which has a high olefin content and is made from readily available and inexpensive raw materials. In addition, it has the characteristics of high olefin content and extremely low sulfur, nitrogen and aromatic hydrocarbon content, resulting in minimal side effects on catalysts and high product selectivity.
[0037] In some embodiments, in step (1), the Fischer-Tropsch C6 fraction contains 20-40% by weight of n-alkanes, 30-60% by weight of n-olefins, 10-25% by weight of isoolefins and 1-5% by weight of oxygen-containing compounds.
[0038] In some specific embodiments, in step (1), the Fischer-Tropsch C6 fraction needs to be deoxygenated before the polymerization reaction. The specific deoxygenation process may include soaking the Fischer-Tropsch C6 fraction in a dried and activated molecular sieve for 20-30 hours. The drying and activation process of the molecular sieve is a conventional operation in the art and will not be described in detail here.
[0039] In the method described in this invention, the alkylaluminum can synergistically with the supported metal to achieve efficient polymerization of the Fischer-Tropsch C6 fraction, improving the selectivity and yield of the isomeric dodecene. Preferably, the alkylaluminum is selected from at least one of triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum. In a further preferred embodiment, the alkylaluminum is triisobutylaluminum.
[0040] In the method described in this invention, the supported metal can provide a catalytically active center, synergistically catalyzing with the alkylaluminum to achieve efficient polymerization of the Fischer-Tropsch C6 fraction, thereby improving the selectivity and yield of the isomeric dodecene. Preferably, the supported metal contains a transition metal element, and the transition metal element is iron, zinc, cobalt, nickel, copper, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, molybdenum, or technetium. In a further preferred embodiment, the supported metal contains titanium.
[0041] In this invention, the type of supporting metal is not limited. Various supporting metals commonly used in the art can be used. Preferably, the supporting metal is at least one of a water-soluble metal halide, oxide, sulfate, and nitrate. More preferably, the supporting metal is a metal halide.
[0042] In some embodiments, in step (1), in order to achieve efficient polymerization of the Fischer-Tropsch C6 fraction and improve the selectivity and yield of the isomeric dodecene, preferably, the weight ratio of the supported metal to the Fischer-Tropsch C6 fraction is 1:10-10000, more preferably 1:12-500, more preferably 1:15-100, and even more preferably 1:20-60. As a specific example, the weight ratio of the supported metal to the Fischer-Tropsch C6 fraction can be 1:20, 1:30, 1:40, 1:50, or 1:60.
[0043] In some embodiments, in step (1), in order to achieve efficient polymerization of the Fischer-Tropsch C6 fraction and improve the selectivity and yield of the isomeric dodecene, preferably, the molar ratio of the supported metal to the alkyl aluminum is 1:1-100, more preferably 1:2-50, more preferably 1:4-20, and even more preferably 1:5-10. As a specific example, the molar ratio of the supported metal to the alkyl aluminum can be 1:5, 1:6, 1:7, 1:8, or 1:10.
[0044] In some embodiments, in step (1), in order to ensure the smooth progress of the polymerization reaction and improve the conversion rate of the Fischer-Tropsch C6 fraction and the yield of the isododecene, it is necessary to limit the amount of hydrogen used. This invention limits the amount of hydrogen used by limiting the pressure of the reaction system after the hydrogen is introduced. Specifically, the pressure of the reaction system after the hydrogen is introduced is preferably 0.5-1.5 MPaG, more preferably 0.8-1.2 MPaG.
[0045] In some specific embodiments, in step (1), the conditions for the polymerization reaction include: a temperature of 25-40°C, preferably 30-38°C; and a time of 2-5 hours, preferably 3-4 hours.
[0046] In the method described in this invention, the type of cobalt catalyst is not limited, and various cobalt catalysts commonly used in the art can be used. Preferably, the cobalt catalyst is selected from at least one of cobalt chloride, cobalt sulfate, cobalt acetate, cobalt carbonate, cobalt nitrate, cobalt oxide, and cobalt octacarbonyl. In a further preferred embodiment, the cobalt catalyst is cobalt octacarbonyl.
[0047] In the method described in this invention, the bisphosphine ligand can synergistically enhance the activity of the hydroformylation reaction and the selectivity of the isotridecyl aldehyde, thereby further improving the yield of the isotridecyl alcohol. Preferably, the bisphosphine ligand is 6,6′-[(3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-diphenyl-2,2′-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxophosphatane) (Biphephos) and / or 4,5-bis(diphenylphosphino)-9,9-dimethyloxanthracene (Xantphos). More preferably, the bisphosphine ligand is Biphephos. In this invention, the structure of Biphephos is shown in Formula (I), and the structure of Xantphos is shown in Formula (II).
[0048]
[0049] In some embodiments, in step (2), based on the total weight of the isododecene, the cobalt catalyst, and the bisphosphine ligand, the content of the cobalt catalyst can be 0.1-1.3 wt%, preferably 0.2-1 wt%, and more preferably 0.3-0.8 wt%. Specifically, based on the total weight of the isododecene, the cobalt catalyst, and the bisphosphine ligand, the content of the cobalt catalyst can be 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, or 0.8 wt%.
[0050] In some embodiments, in step (2), to improve the activity of the hydroformylation reaction and the selectivity of the isotridecylaldehyde, thereby further improving the yield of the isotridecyl alcohol, preferably, the molar ratio of the bisphosphine ligand to the cobalt catalyst is 1:0.3-5, more preferably 1:0.5-4, and even more preferably 1:0.8-3. As a specific example, the molar ratio of the bisphosphine ligand to the cobalt catalyst can be 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, or 1:3.
[0051] In some embodiments, in step (2), to ensure the smooth progress of the hydroformylation reaction, improve the selectivity of the isotridecylaldehyde, and thus further improve the yield of the isotridecyl alcohol, it is necessary to limit the amount of syngas used. This invention limits the amount of syngas used by limiting the initial pressure of the reaction system after the syngas is introduced. Specifically, the initial pressure of the reaction system after the syngas is introduced is preferably 1-15 MPaG, more preferably 1-10 MPaG, and even more preferably 1-6 MPaG.
[0052] In some specific embodiments, in step (2), in order to further improve the yield of the isotridecaldehyde and thus further improve the yield of the isotridecyl alcohol, in a preferred case, the volume ratio of H2 to CO in the synthesis gas is 0.9-3.5:1, preferably 1-3:1.
[0053] In some specific embodiments, in step (2), the conditions for the hydroformylation reaction include: a temperature of 85-220°C, preferably 90-200°C; a pressure of 1-15 MPaG, preferably 1.5-5 MPaG; and a time of 2-10 h, preferably 4-8 h.
[0054] In some embodiments, in step (3), in order to ensure the smooth progress of the aldehyde hydrogenation reaction, improve the selectivity of the isotridecyl alcohol, and thus further improve the yield of the isotridecyl alcohol, it is necessary to limit the amount of hydrogen used. This invention controls the amount of hydrogen used by limiting the pressure of the reaction system after the hydrogen is introduced. Specifically, the hydrogen is introduced to make the pressure of the reaction system 0.5-5 MPaG, more preferably 1-4 MPaG, and even more preferably 2-3.5 MPaG.
[0055] In some embodiments, in step (3), in order to ensure the smooth progress of the aldehyde hydrogenation reaction and improve the selectivity of the isotridecyl alcohol, thereby further improving the yield of the isotridecyl alcohol, in a preferred case, the liquid hourly space velocity of the isotridecyl alcohol is 0.5-8 hr. -1 Preferably 1-5 hours -1 Further preferably 1-3 hours -1 .
[0056] In the method described in this invention, the type of hydrogenation catalyst is not limited, and various hydrogenation catalysts commonly used in the art can be used. Preferably, the hydrogenation catalyst is selected from at least one of copper-zinc catalysts, nickel-based catalysts, and palladium-based catalysts. More preferably, the hydrogenation catalyst is a nickel-based catalyst. In some specific embodiments, the hydrogenation catalyst is an alumina-supported nickel catalyst containing alumina, silicon dioxide, and nickel, wherein the silicon dioxide content is 4-8 wt%, the nickel content is 10-20 wt%, and the remainder is alumina.
[0057] In some specific embodiments, in step (3), the conditions for the aldehyde hydrogenation reaction include: 100-200℃, preferably 120-180℃.
[0058] The following examples further illustrate the method for preparing isomeric tridecanol from Fischer-Tropsch olefins according to the present invention. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.
[0059] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.
[0060] In the following examples and comparative examples, the feedstock for the Fischer-Tropsch C6 fraction was oil-washed naphtha, a product of coal-to-oil Fischer-Tropsch synthesis, obtained by distillation and cutting, wherein the content of n-alkanes was 21.5% by weight, the content of n-olefins was 58% by weight, the content of isoolefins was 19% by weight, and the content of oxygen-containing compounds was 1.5% by weight.
[0061] The molecular sieve used was 3A molecular sieve, purchased from Tianjin Kemeo Chemical Reagent Co., Ltd.
[0062] The alumina-supported nickel catalyst contains aluminum oxide, silicon dioxide and nickel, wherein the silicon dioxide content is 5 wt%, the nickel content is 16 wt%, and the remainder is alumina.
[0063] Example 1
[0064] (1) The polymerization reactor was first thoroughly cleaned with anhydrous ethanol, then the reactor was evacuated to a negative pressure (≤1kPa), and then replaced with nitrogen gas multiple times. After the replacement was completed, the dew point inside the reactor was measured by an air dew point meter to ensure that the dew point inside the reactor was ≤-65℃. The C6 fraction was soaked in the dried and activated 3A molecular sieve for 24h. Titanium tetrachloride was distilled under nitrogen protection. The deoxidized C6 fraction, triisobutylaluminum and distilled titanium tetrachloride were added to the polymerization reactor in sequence. Then hydrogen gas was introduced into the reactor until the pressure inside the reactor was 1MPaG. Circulating water was introduced to maintain the temperature inside the reactor at 35℃. The reaction was carried out for 3.5h. After the reaction was completed, 1% of antioxidant alcohol 264 was added to terminate the reaction. The reaction product was distilled to obtain isomeric dodecene. The weight ratio of distilled titanium tetrachloride to deoxidized C6 fraction was 1:40, and the molar ratio of distilled titanium tetrachloride to triisobutylaluminum was 1:7.
[0065] (2) 600g of isododecene, cobalt octacarbonyl and Biphephos were added to the reactor, and syngas was introduced until the pressure inside the reactor was 2MPaG. After heating to 100℃, the reaction was stirred and carried out for 5h to obtain isotridecaldehyde. The content of cobalt octacarbonyl was 0.5% by weight, based on the total weight of isododecene, cobalt octacarbonyl and Biphephos. The molar ratio of Biphephos to cobalt octacarbonyl was 1:1. The volume ratio of H2 to CO in the syngas was 1:1.
[0066] (3) An alumina-supported nickel catalyst is loaded into a fixed-bed reactor, and hydrogen gas is introduced until the reactor pressure reaches 3 MPaG. The isomeric tridecanal is then transferred to a fixed-bed reactor loaded with a nickel-based catalyst and reacted at 150°C to obtain crude isomeric tridecanol. The resulting reaction product is then distilled to obtain isomeric tridecanol. The liquid hourly space velocity (LHSV) of the isomeric tridecanal is 2 hr. -1 .
[0067] Example 2
[0068] (1) The polymerization reactor was first thoroughly cleaned with anhydrous ethanol, then the reactor was evacuated to a negative pressure (≤1kPa), and then replaced with nitrogen gas multiple times. After the replacement was completed, the dew point inside the reactor was measured by an air dew point meter to ensure that the dew point inside the reactor was ≤-65℃. The C6 fraction was soaked in the dried and activated 3A molecular sieve for 24h. Titanium tetrachloride was distilled under nitrogen protection. The deoxidized C6 fraction, triisobutylaluminum and distilled titanium tetrachloride were added to the polymerization reactor in sequence. Then hydrogen gas was introduced into the reactor until the pressure inside the reactor was 0.8MPaG. Circulating water was introduced to maintain the temperature inside the reactor at 30℃. The reaction was carried out for 4h. After the reaction was completed, 1% of antioxidant alcohol 264 was added to terminate the reaction. The reaction product was distilled to obtain isomeric dodecene. The weight ratio of distilled titanium tetrachloride to deoxidized C6 fraction was 1:20, and the molar ratio of distilled titanium tetrachloride to triisobutylaluminum was 1:5.
[0069] (2) 600g of isododecene, cobalt octacarbonyl and Biphephos were added to the reactor, and syngas was introduced until the pressure inside the reactor was 1.5MPaG. After heating to 90℃, the reaction was stirred and carried out for 8h to obtain isodecithal. The content of cobalt octacarbonyl was 0.3% by weight, based on the total weight of isododecene, cobalt octacarbonyl and Biphephos. The molar ratio of Biphephos to cobalt octacarbonyl was 1:0.8. The volume ratio of H2 to CO in the syngas was 2:1.
[0070] (3) An alumina-supported nickel catalyst is loaded into a fixed-bed reactor, and hydrogen gas is introduced until the reactor pressure reaches 2 MPaG. The isotridecaldehyde is then transferred to a fixed-bed reactor packed with a nickel-based catalyst. Crude isotridecyl alcohol is obtained at 120°C. The resulting reaction product is then distilled to obtain isotridecyl alcohol. The liquid hourly space velocity (LISH) of the isotridecaldehyde fraction is 1 hr. -1 .
[0071] Example 3
[0072] (1) The polymerization reactor was first thoroughly cleaned with anhydrous ethanol, then the reactor was evacuated to a negative pressure (≤1kPa), and then replaced with nitrogen gas multiple times. After the replacement was completed, the dew point inside the reactor was measured by an air dew point meter to ensure that the dew point inside the reactor was ≤-65℃. The C6 fraction was soaked in the dried and activated 3A molecular sieve for 24h. Titanium tetrachloride was distilled under nitrogen protection. The deoxidized C6 fraction, triisobutylaluminum and distilled titanium tetrachloride were added to the polymerization reactor in sequence. Then hydrogen gas was introduced into the reactor until the pressure inside the reactor was 1MPaG. Circulating water was introduced to maintain the temperature inside the reactor at 38℃. The reaction was carried out for 3h. After the reaction was completed, 1% of antioxidant alcohol 264 was added to terminate the reaction. The reaction product was distilled to obtain isomeric dodecene. The weight ratio of distilled titanium tetrachloride to deoxidized C6 fraction was 1:60, and the molar ratio of distilled titanium tetrachloride to triisobutylaluminum was 1:10.
[0073] (2) 600g of isododecene, cobalt octacarbonyl and Biphephos were added to the reactor, and syngas was introduced until the pressure inside the reactor was 5MPaG. After heating to 200℃, the reaction was stirred and carried out for 4h to obtain isotridecaldehyde. The content of cobalt octacarbonyl was 0.8% by weight, based on the total weight of isododecene, cobalt octacarbonyl and Biphephos. The molar ratio of Biphephos to cobalt octacarbonyl was 1:3. The volume ratio of H2 to CO in the syngas was 3:1.
[0074] (3) An alumina-supported nickel catalyst is loaded into a fixed-bed reactor, and hydrogen gas is introduced until the reactor pressure reaches 3.5 MPaG. The isotridecaldehyde is then transferred to a fixed-bed reactor packed with a nickel-based catalyst. Crude isotridecyl alcohol is obtained at 180°C. The resulting reaction product is then distilled to obtain isotridecyl alcohol. The liquid hourly space velocity (LISH) of the isotridecaldehyde fraction is 3 h⁻¹. -1 .
[0075] Example 4
[0076] The preparation was carried out according to the method described in Example 1, except that in step (1), the weight ratio of the distilled titanium tetrachloride to the deoxidized C6 fraction was 1:9.
[0077] Example 5
[0078] The preparation was carried out according to the method described in Example 1, except that in step (1), the molar ratio of distilled titanium tetrachloride and triisobutylaluminum was 1:0.9.
[0079] Example 6
[0080] The preparation was carried out according to the method described in Example 1, except that in step (2), the content of cobalt octacarbonyl was 0.1% based on the total weight of isododecene, cobalt octacarbonyl and Biphephos.
[0081] Example 7
[0082] The preparation was carried out according to the method described in Example 1, except that in step (2), the molar ratio of Biphephos and octacarbonyl dicobalt was 1:6.
[0083] Example 8
[0084] The preparation was carried out according to the method described in Example 1, except that in step (1), triisopropylaluminum was used instead of triisobutylaluminum in an equimolar amount.
[0085] Example 9
[0086] The preparation was carried out according to the method described in Example 6, except that in step (2), cobalt chloride was used instead of cobalt octacarbonyl in equal parts by weight.
[0087] Example 10
[0088] The preparation was carried out according to the method described in Example 1, except that in step (2), an equimolar amount of Xantphos was used instead of Biphephos.
[0089] Comparative Example 1
[0090] The preparation was carried out according to the method described in Example 1, except that in step (1), equal amounts of diisobutylaluminum and ferric chloride were used instead of diisobutylaluminum and distilled titanium tetrachloride.
[0091] Comparative Example 2
[0092] The preparation was carried out according to the method described in Example 1, except that in step (2), cobalt carbonate and triphenylphosphine were used in place of cobalt octacarbonyl and Biphephos.
[0093] Test case
[0094] Test Example 1
[0095] (1) In this invention, a gas chromatograph (purchased from Shimadzu Corporation, Japan, model GC-2014) was used to analyze the composition of the polymerization reaction raw materials and the composition of the polymerization products in the examples and comparative examples. The yield of isomeric dodecene was obtained by calculating step (1) using the following formula. The results are shown in Table 1.
[0096] A = [(A1-A2) / A1] × 100%
[0097] In the formula, A represents the C6 olefin conversion rate, A1 represents the mass fraction of C6 olefins in the feedstock before the reaction, and A2 represents the mass fraction of unreacted C6 olefins in the reactor outlet product.
[0098] (2) The present invention uses the above-mentioned gas chromatograph to analyze the composition of raw materials and hydroformylation products before and after hydroformylation reaction in the examples and comparative examples, and calculates the conversion rate of isododecene and the yield of isotridecaldehyde by the following formula in step (2), and the results are shown in Table 1.
[0099] B = [(B1-B2) / B1] × 100%
[0100] In the formula, B represents the conversion rate of isododecene, B1 represents the mass fraction of isododecene in the raw material before the reaction, and B2 represents the mass fraction of unreacted isododecene in the product after the reaction.
[0101] (3) The present invention uses the above-mentioned gas chromatograph to analyze the composition of hydrogenation raw materials and hydrogenation products in the examples and comparative examples, and calculates the conversion rate of isotridecaldehyde, the selectivity of isotridecaldehyde and the yield of isotridecaldehyde by the following formula in step (3). The results are shown in Table 1.
[0102] C = [(C1-C2) / C1] × 100%
[0103] D = [D1 / (D1+D2)] × 100%
[0104] In the formula, C represents the conversion rate of isotretinoin, C1 represents the mass fraction of isotretinoin in the raw material before the reaction, and C2 represents the mass fraction of unreacted isotretinoin in the reactor outlet product; D represents the selectivity of isotretinoin, D1 represents the mass fraction of isotretinoin in the outlet product, and D2 represents the mass fraction of by-products in the reactor outlet product.
[0105] Table 1
[0106]
[0107]
[0108] As can be seen from the results in Table 1, this method has the advantages of readily available raw materials, high conversion rate, good selectivity, high yield of isomeric tridecanol, mild reaction conditions, and strong process stability. In addition, the method is simple and convenient to operate, has good economic benefits, and is highly compatible with the needs of large-scale industrial production, showing significant economic value and broad industrial application prospects.
[0109] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A method for preparing isomeric tridecanol from Fischer-Tropsch olefins, characterized in that, The method includes the following steps: (1) Mix the Fischer-Tropsch C6 fraction, alkyl aluminum and supported metal, and then pass hydrogen into the resulting mixture to carry out a polymerization reaction to obtain isomeric dodecene. (2) Mix the isododecene, cobalt catalyst and bisphosphine ligand, and then introduce syngas into the resulting reaction mixture to carry out hydroformylation reaction to obtain isotridecaldehyde. (3) In the presence of a hydrogenation catalyst, the isomeric tridecanal is mixed with hydrogen to carry out an aldehyde hydrogenation reaction; The alkylaluminum is selected from at least one of triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, and triisobutylaluminum; The metal element contained in the load metal is a transition metal element.
2. The method according to claim 1, characterized in that, The transition metal element is iron, zinc, cobalt, nickel, copper, scandium, titanium, vanadium, chromium, manganese, yttrium, zirconium, molybdenum, or technetium; and / or The loaded metal is at least one of water-soluble metal halides, oxides, sulfates, and nitrates.
3. The method according to claim 1 or 2, characterized in that, In step (1), the weight ratio of the loaded metal to the Fischer-Tropsch C6 fraction is 1:10-10000; and / or The molar ratio of the loaded metal to the alkyl aluminum is 1:1-100.
4. The method according to any one of claims 1-3, characterized in that, In step (1), the Fischer-Tropsch C6 fraction contains 20-40% by weight of n-alkanes, 30-60% by weight of n-olefins, 10-25% by weight of isoolefins and 1-5% by weight of oxygen-containing compounds.
5. The method according to any one of claims 1-4, characterized in that, In step (1), hydrogen gas is introduced to make the pressure of the reaction system 0.5-1.5 MPaG; and / or The conditions for the polymerization reaction include: a temperature of 25-40℃ and a time of 2-5 hours.
6. The method according to claim 1, characterized in that, In step (2), the content of the cobalt catalyst is 0.1-1.3% by weight, based on the total weight of the isododecene, the cobalt catalyst, and the bisphosphine ligand; and / or The molar ratio of the bisphosphine ligand to the cobalt catalyst is 1:0.3-5; and / or The cobalt catalyst is selected from at least one of cobalt chloride, cobalt sulfate, cobalt acetate, cobalt carbonate, cobalt nitrate, cobalt oxide, and cobalt octacarbonyl; and / or The bisphosphine ligand is 6,6′-[(3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-diphenyl-2,2′-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxaheptaene) and / or 4,5-bis(diphenylphosphino)-9,9-dimethyloxanthracene.
7. The method according to claim 1 or 6, characterized in that, In step (2), the synthesis gas is introduced to bring the initial pressure of the reaction system to 1-15 MPaG; and / or In the synthesis gas, the volume ratio of H2 to CO is 0.9-3.5:
1.
8. The method according to claim 1, 6, or 7, characterized in that, In step (2), the conditions for the hydroformylation reaction include: a temperature of 85-220°C, a pressure of 1-15 MPaG, and a time of 2-10 h.
9. The method according to claim 1, characterized in that, In step (3), hydrogen gas is introduced to make the pressure of the reaction system 0.5-5 MPaG; and / or The liquid hourly space velocity (LISH) of the isomeric tridecanal is 0.5-8 hr. -1 ; and / or The hydrogenation catalyst is selected from at least one of copper-zinc catalysts, nickel-based catalysts, and palladium-based catalysts.
10. The method according to claim 1 or 9, characterized in that, In step (3), the conditions for the aldehyde hydrogenation reaction include a temperature of 100-200℃.