Synthesis method of iso-tridecanol
By using Fischer-Tropsch olefins from C5 to 6, the problem of low yield of isomeric tridecanol is solved, and an efficient and economical isomeric tridecanol production process is achieved.
Patent Information
- Application Number
- CN202411685186.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-22
- Publication Date
- 2025-02-18
AI Technical Summary
In the prior art, the yield of isomer tridecanol is low, and the reaction conditions during the production process are harsh, energy consumption is high, and economical is poor.
Isomeric tridecanol is synthesized by carbonylation, condensation and hydrogenation reactions of C5-6 Fischerol olefins, and the condensation reaction is carried out in a microchannel reactor to improve the reaction efficiency and selectivity.
The yield and purity of isomeric tridecanol is improved, production costs are reduced, and the use of microchannel reactors optimizes mass and heat transfer effects, and reduces the generation of by-products.
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Figure BDA0005149251400000081
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for synthesizing isomeric tridecanol. Background Art
[0002] Isotridecyl alcohol is a synthetic alcohol that is easily soluble in water, resistant to acids and alkalis, corrosion-resistant, completely biodegradable, and has good surface activity. It is mainly used in industries such as textile auxiliaries, antioxidants, and metal processing auxiliaries. As the national environmental protection policy becomes increasingly stringent, isotridecyl alcohol is popular due to its low toxicity, good penetration, high emulsification, safety, environmental protection, and easy degradation. At the same time, the scope of application of isotridecyl alcohol is constantly expanding, and the market penetration rate of isotridecyl alcohol antioxidants will continue to increase, and the market demand will also continue to grow.
[0003] The main production method of isomeric tridecanol is that butene trimerization or propylene tetramerization obtains isododecene, and then carbonyl synthesis and hydrogenation are carried out to obtain isomeric tridecanol. The raw materials butene and propylene used in the current production of isomeric tridecanol require higher purity, and butene and propylene cannot be highly selectively oligomerized to generate trimerized butene and tetrapropylene, resulting in a low yield of isomeric dodecene, thereby making the yield of isomeric tridecanol low. The olefin hydroformylation reaction conditions of high carbon number are harsh, energy consumption is high, and economy is poor. There is poor mass transfer and heat transfer effect in ordinary autoclave condensation reactor, resulting in poor quality of reaction product, low reaction efficiency, and long reaction time. Therefore, it is necessary to develop a kind of high selectivity, high yield of isomeric tridecanol preparation method. Summary of the invention
[0004] The main purpose of the present invention is to provide a method for synthesizing isomeric tridecanol to solve the problem of low yield of isomeric tridecanol in the prior art.
[0005] In order to achieve the above object, according to one aspect of the present invention, a method for synthesizing isomeric tridecanol is provided, the method comprising: step S1, 5～6 The Fischer-Tropsch olefins react with the synthesis gas under the action of the carbonylation catalyst to obtain C 6～7 Step S2, C 6～7 The aldehyde is subjected to a condensation reaction under the action of a condensation catalyst to obtain isomeric tridecene aldehyde; step S3, the isomeric tridecene aldehyde is subjected to a hydrogenation reaction under the action of a hydrogenation catalyst to obtain isomeric tridecanol; wherein the condensation reaction is carried out in a microchannel reactor.
[0006] Furthermore, in the above step S2, the microchannel reactor is a coil-type microchannel reactor, the tube length of the coil-type microchannel reactor is 10 to 50 m; and / or, the inner diameter of the tube of the coil-type microchannel reactor is 3 to 8 mm; and / or, the condensation reaction is continuously carried out in the microchannel reactor, C 6～7The residence time of the aldehyde in the microchannel reactor is 0.1 to 3 hours, preferably 1 to 2 hours; and / or the temperature of the condensation reaction is 90 to 200° C., preferably 140 to 180° C.
[0007] Furthermore, in the above step S2, the condensation catalyst is an inorganic alkali solution and / or an inorganic solid alkali; preferably, the inorganic alkali solution is selected from any one or more of sodium hydroxide solution, potassium hydroxide solution, potassium carbonate solution and sodium carbonate solution; and / or, the inorganic solid alkali is selected from any one or more of sodium oxide, calcium oxide, magnesium oxide and potassium oxide; preferably, the condensation catalyst is an inorganic alkali solution, and the mass concentration of the inorganic alkali solution is 5% to 30%, preferably 10 to 30%, C 6～7 The total feed rate of the aldehyde and inorganic base solution is 1 to 10 mL / min, preferably 3 to 6 mL / min, and C 6～7 The volume ratio of the aldehyde to the inorganic base solution is 1:1 to 5; preferably, C 6～7 The aldehyde and the inorganic base solution are mixed in a mixer and then continuously introduced into a microchannel reactor for condensation reaction.
[0008] Further, in the above step S3, the hydrogenation reaction is carried out in a fixed bed hydrogenation reactor; and / or, the pressure of the hydrogenation reaction is 0.5 to 5.0 MPa, preferably 2.0 to 3.0 MPa; and / or, the temperature of the hydrogenation reaction is 100 to 200° C., preferably 145 to 160° C.; and / or, the feed amount of isomeric tridecene aldehyde is 0.5 g / min to 5 g / min, preferably 1 to 2 g / min; and / or, the loading amount of the hydrogenation catalyst is 40 to 80 g; and / or, the mass space velocity of the hydrogenation reaction is 0.5 to 5 h -1 .
[0009] Furthermore, in the above step S3, the hydrogenation catalyst is selected from any one or more of a copper-zinc catalyst, a nickel-based catalyst and a palladium-based catalyst; preferably, the nickel-based catalyst is selected from any one or more of Ni / MgNO3, Ni / diatomaceous earth and Ni / Ga(NO3)2; and / or, the palladium-based catalyst is Pa / Al2O3 and / or Pa / MgNO3.
[0010] Furthermore, in the above step S1, the temperature of the carbonylation reaction is 85-120°C; and / or, the pressure of the carbonylation reaction is 1-5 MPa; and / or, the time of the carbonylation reaction is 2-10 h; preferably, the temperature of the carbonylation reaction is 100-120°C; and / or, the pressure of the carbonylation reaction is 2-5 MPa; and / or, the time of the carbonylation reaction is 5-10 h.
[0011] Furthermore, in the above step S1, the carbonylation reaction is carried out in a reactor, C 5～6The mass ratio of the Fischer-Tropsch olefin to the carbonylation catalyst is 1:2-5; preferably, the carbonylation catalyst is a rhodium-based catalyst and / or a cobalt-based catalyst; further preferably, the rhodium-based catalyst is selected from any one or more of hydrated rhodium trichloride, dicarbonyl rhodium acetylacetonate, tris(sodium triphenylphosphine tris-metasulfonate) carbonyl rhodium chloride and divinyl rhodium acetylacetonate; and / or, the cobalt-based catalyst is selected from any one or more of octacarbonyl dicobalt, cobalt octoate and cobalt chloride hexahydrate.
[0012] Further, in parts by weight, the above C 5～6 The Fischer-Tropsch olefins include: 25 to 40 parts of normal alkanes, 25 to 60 parts of normal olefins, 10 to 25 parts of isoolefins and 1 to 5 parts of oxygen-containing compounds.
[0013] Furthermore, the above-mentioned synthesis method comprises: in step S2, the product of the condensation reaction is separated in a phase separator to obtain isomeric tridecene aldehyde.
[0014] Furthermore, the above-mentioned synthesis method comprises: in step S3, the product of the hydrogenation reaction is subjected to distillation treatment to obtain isomeric tridecanol.
[0015] Applying the technical solution of the present invention, this application adopts C 5～6 The preparation of isomeric tridecanol from Fischer-Tropsch olefins is helpful to enrich the raw material sources for the synthesis of isomeric tridecanol, and C 5～6 The Fischer-Tropsch olefins are more easily available and at a lower cost. The condensation reaction in step S2 is carried out in a microchannel reactor. Compared with traditional kettle reactors and fixed bed reactors, microchannel reactors have significant mass transfer and heat transfer advantages, which can greatly improve the reaction efficiency and selectivity. The use of microchannel reactors helps to promote uniform mixing and contact of materials, so that the condensation catalyst and C 6～7 The mass transfer process between the aldehydes is more efficient, which helps to avoid the formation of by-products caused by local overheating, helps to increase the yield of isomeric tridecene aldehyde, and further helps to increase the yield of the final product isomeric tridecene alcohol. DETAILED DESCRIPTION
[0016] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail with reference to the embodiments below.
[0017] As analyzed in the background technology of the present application, the prior art has the problem of low yield of isomeric tridecanol. In order to solve the above problem, the present application provides a method for synthesizing isomeric tridecanol.
[0018] It should be noted that synthesis gas refers to a gas in which the volume ratio of H2 and CO is 1:1.
[0019] In a typical embodiment of the present application, a method for synthesizing isomeric tridecanol is provided, the method comprising: step S1, 5～6 The Fischer-Tropsch olefins react with the synthesis gas under the action of the carbonylation catalyst to obtain C 6～7 Step S2, C 6～7 The aldehyde is subjected to a condensation reaction under the action of a condensation catalyst to obtain isomeric tridecene aldehyde; step S3, the isomeric tridecene aldehyde is subjected to a hydrogenation reaction under the action of a hydrogenation catalyst to obtain isomeric tridecanol; wherein the condensation reaction is carried out in a microchannel reactor.
[0020] This application adopts C 5～6 The preparation of isomeric tridecanol from Fischer-Tropsch olefins is helpful to enrich the raw material sources for the synthesis of isomeric tridecanol, and C 5～6 The Fischer-Tropsch olefins are more easily available and at a lower cost. The condensation reaction in step S2 is carried out in a microchannel reactor. Compared with traditional kettle reactors and fixed bed reactors, microchannel reactors have significant mass transfer and heat transfer advantages, which can greatly improve the reaction efficiency and selectivity. The use of microchannel reactors helps to promote uniform mixing and contact of materials, so that the condensation catalyst and C 6～7 The mass transfer process between the aldehydes is more efficient, which helps to avoid the formation of by-products caused by local overheating, helps to increase the yield of isomeric tridecene aldehyde, and further helps to increase the yield of the final product isomeric tridecene alcohol.
[0021] In one embodiment of the present application, in the above step S2, the microchannel reactor is a coil-type microchannel reactor, the tube length of the coil-type microchannel reactor is 10 to 50 m; and / or, the inner diameter of the tube of the coil-type microchannel reactor is 3 to 8 mm; and / or, the condensation reaction is continuously carried out in the microchannel reactor, C 6～7 The residence time of the aldehyde in the microchannel reactor is 0.1 to 3 hours, preferably 1 to 2 hours; and / or the temperature of the condensation reaction is 90 to 200° C., preferably 140 to 180° C.
[0022] It is preferred to control the tube length and the inner diameter of the microchannel reactor within the above range, which helps to further improve the uniform mixing and contact of the materials, thereby helping to improve the condensation catalyst and C 6～7 The mass transfer efficiency between the aldehydes is preferably controlled within the above range. The residence time of the condensation reaction is preferably controlled within the above range, which helps to reduce the occurrence of side reactions while improving the reaction efficiency. The temperature of the condensation reaction is preferably controlled within the above range, which helps to reduce the occurrence of side reactions while improving the activity of the condensation catalyst.
[0023] Including but not limited to, the material of the tubes in the above-mentioned coil-type microchannel reactor is stainless steel.
[0024] In one embodiment of the present application, in the above step S2, the condensation catalyst is an inorganic alkali solution and / or an inorganic solid alkali; preferably, the inorganic alkali solution is selected from any one or more of sodium hydroxide solution, potassium hydroxide solution, potassium carbonate solution and sodium carbonate solution; and / or, the inorganic solid alkali is selected from any one or more of sodium oxide, calcium oxide, magnesium oxide and potassium oxide; preferably, the condensation catalyst is an inorganic alkali solution, and the mass concentration of the inorganic alkali solution is 5% to 30%, preferably 10 to 30%, C 6～7 The total feed rate of the aldehyde and inorganic base solution is 1 to 10 mL / min, preferably 3 to 6 mL / min, and C 6～7 The volume ratio of the aldehyde to the inorganic base solution is 1:1 to 5; preferably, C 6～7 The aldehyde and the inorganic base solution are mixed in a mixer and then continuously introduced into a microchannel reactor for condensation reaction.
[0025] Inorganic base catalysts provide an alkaline environment in the condensation reaction, which helps promote the 6～7 A condensation reaction is carried out between aldehyde molecules. A higher concentration of inorganic alkali solution helps to provide a stronger alkaline environment and accelerate the process of the condensation reaction, but too high a concentration may cause unnecessary side reactions. In addition, inorganic alkali solutions are more convenient to carry out continuous reactions in microchannel reactors than inorganic solid alkalis, thereby helping to improve the efficiency of the condensation reaction. It is preferred to control C 6～7 The total feed amount of the aldehyde and the inorganic base solution is within the above range, which helps to reduce the probability of incomplete reaction due to excessive feed. 6～7 The volume ratio of the aldehyde to the inorganic base solution is within the above range, which helps to improve the effective contact between the reactants and the catalyst, thereby helping to improve the selectivity and conversion rate of the reaction. 6～7 The aldehyde and the inorganic base solution are mixed in a mixer and then introduced into a microchannel reactor, which helps to improve the reaction efficiency and thus helps to improve the yield of isomeric tridecanol.
[0026] In one embodiment of the present application, in the above step S3, the hydrogenation reaction is carried out in a fixed bed hydrogenation reactor; and / or, the pressure of the hydrogenation reaction is 0.5-5.0 MPa, preferably 2.0-3.0 MPa; and / or, the temperature of the hydrogenation reaction is 100-200°C, preferably 145-160°C; and / or, the feed amount of isomeric tridecene aldehyde is 0.5 g / min-5 g / min, preferably 1-2 g / min; and / or, the loading amount of the hydrogenation catalyst is 40-80 g; and / or, the mass space velocity of the hydrogenation reaction is 0.5-5 h -1 .
[0027] Higher pressure in hydrogenation reaction is conducive to improving the solubility and reaction rate of hydrogen, and promotes the hydrogenation saturation of olefins. However, too high pressure will increase equipment cost and operational complexity, and preferably the pressure of hydrogenation reaction is controlled within the above range, which helps to reduce production cost while improving reaction efficiency. Preferably, the temperature of hydrogenation reaction is controlled within the above range, which helps to reduce the generation of side reactions while improving reaction rate, thereby helping to improve the purity and selectivity of product. Preferably, the feed amount of isomeric tridecene aldehyde is controlled within the above range, which helps to improve the efficiency of hydrogenation reaction. Preferably, the loading amount of hydrogenation catalyst is controlled within the above range, which helps to promote the full contact of isomeric tridecene aldehyde with hydrogenation catalyst, thereby helping to improve the efficiency of hydrogenation reaction. Preferably, the mass space velocity of hydrogenation reaction is controlled within the above range, which helps to improve the selectivity and yield of isomeric tridecene alcohol.
[0028] In order to further improve the efficiency of the hydrogenation reaction, in one embodiment of the present application, preferably in the above step S3, the hydrogenation catalyst is selected from any one or more of a copper-zinc catalyst, a nickel-based catalyst and a palladium-based catalyst; preferably, the nickel-based catalyst is selected from any one or more of Ni / MgNO3, Ni / diatomaceous earth and Ni / Ga(NO3)2; and / or, the palladium-based catalyst is Pa / Al2O3 and / or Pa / MgNO3.
[0029] In one embodiment of the present application, in the above step S1, the temperature of the carbonylation reaction is 85-120°C; and / or, the pressure of the carbonylation reaction is 1-5 MPa; and / or, the time of the carbonylation reaction is 2-10 h; preferably, the temperature of the carbonylation reaction is 100-120°C; and / or, the pressure of the carbonylation reaction is 2-5 MPa; and / or, the time of the carbonylation reaction is 5-10 h.
[0030] If the temperature is too low, the carbonylation reaction rate will be too slow, and if the temperature is too high, it will easily lead to the occurrence of side reactions. It is preferred to control the temperature of the carbonylation reaction within the above range, which will help to increase the reaction rate while reducing the occurrence of side reactions. It is preferred to control the pressure and time of the carbonylation reaction within the above range, which will help to increase the carbonylation reaction rate. 6～7 The yield of aldehyde.
[0031] In order to further improve C 6～7 In one embodiment of the present application, preferably in the above step S1, the carbonylation reaction is carried out in a reactor, C 5～6The mass ratio of the Fischer-Tropsch olefin to the carbonylation catalyst is 1:2-5; preferably, the carbonylation catalyst is a rhodium-based catalyst and / or a cobalt-based catalyst; further preferably, the rhodium-based catalyst is selected from any one or more of hydrated rhodium trichloride, dicarbonyl rhodium acetylacetonate, tris(sodium triphenylphosphine tris-metasulfonate) carbonyl rhodium chloride and divinyl rhodium acetylacetonate; and / or, the cobalt-based catalyst is selected from any one or more of octacarbonyl dicobalt, cobalt octoate and cobalt chloride hexahydrate. The carbonylation catalyst can be recycled.
[0032] In one embodiment of the present application, the above C 5～6 The Fischer-Tropsch olefins include: 25 to 40 parts of normal alkanes, 25 to 60 parts of normal olefins, 10 to 25 parts of isoolefins and 1 to 5 parts of oxygen-containing compounds (such as alcohols, ketones, carboxylic acids, etc.).
[0033] C 5～6 The Fischer-Tropsch olefins contain the above components, and the weight fraction of each component has a wide range. As a raw material for synthesizing isomeric tridecanol, it helps to increase the source of raw materials and reduce the dependence on specific high-purity raw materials.
[0034] In one embodiment of the present application, the above-mentioned synthesis method comprises: in step S2, the product of the condensation reaction is separated in a phase separator to obtain isomeric tridecene aldehyde.
[0035] The product of the condensation reaction is introduced into a phase separator, which can effectively separate the isomeric tridecene aldehyde generated by the reaction from the reaction medium, unreacted raw materials and by-products. This process helps to improve the purity of the isomeric tridecene aldehyde and provide higher quality raw materials for the subsequent hydrogenation reaction. The improvement in purity helps to reduce the complexity and cost of subsequent processing steps, and also helps to improve the quality of the final product, isomeric tridecene alcohol.
[0036] In one embodiment of the present application, the above-mentioned synthesis method includes: in step S3, the product of the hydrogenation reaction is subjected to distillation treatment to obtain isomeric tridecanol.
[0037] Using distillation to remove impurities helps to simplify subsequent processing steps and reduce dependence on other purification methods, such as adsorption and extraction, thereby helping to save time and costs, simplify operating procedures and improve production efficiency.
[0038] The beneficial effects of the present application will be further illustrated below in conjunction with embodiments.
[0039] Example 1
[0040] (1) Hydroformylation: by weight, C 5～6The Fischer-Tropsch olefins include: 40 parts of normal alkanes, 60 parts of normal olefins, 25 parts of isoolefins and 5 parts of oxygen-containing compounds. 5～6 1000 g of Fischer-Tropsch olefin and 1000 g of hydrated rhodium trichloride were added to the reactor, and synthesis gas (the volume ratio of H2 to CO was 1:1) was introduced. The temperature was raised to 100°C and the reaction pressure was 2 MPa. The stirring reaction was started and the reaction was continued for 5 h to obtain C 6～7 of aldehyde.
[0041] (2) Aldol condensation: Prepare an inorganic alkali solution catalyst, wherein the inorganic alkali in the inorganic alkali solution is potassium hydroxide, and the mass concentration of the inorganic alkali solution is 5%. 6～7 The aldehyde and catalyst were mixed in a T-type micromixer. 6～7 The volume ratio of the aldehyde and the catalyst is 1:1, and the mixed solution is then transported to a coil-type microchannel reactor at a flow rate of 3 mL / min for condensation reaction. The length of the coil-type microchannel reactor is 10 m, the inner diameter of the coil-type microchannel reactor is 3 mm, the residence time of the condensation reaction is 2 h, and the temperature of the condensation reaction is 140 ° C. After the reaction is completed, it enters a phase separator to obtain isomeric tridecene aldehyde.
[0042] (3) Hydrogenation and refining: A fixed bed reactor was used for hydrogenation. The feed rate of isomeric tridecene aldehyde was 2.0 g / min, the reaction temperature was 160°C, the reaction pressure was 3 MPa, the nickel catalyst (nickel nitrate hexahydrate) was loaded in an amount of 40 g, and the mass space velocity was 2.5 h -1 The obtained crude isomeric tridecanol is subjected to distillation to obtain isomeric tridecanol.
[0043] Example 2
[0044] (1) Hydroformylation: by weight, C 5～6 The Fischer-Tropsch olefins include: 25 parts of normal alkanes, 25 parts of normal olefins, 10 parts of isoolefins and 1 part of oxygen-containing compounds. 5～6 1000 g of Fischer-Tropsch olefin and 1000 g of divinyl rhodium acetylacetonate were added to the reactor, and synthesis gas (the volume ratio of H2 to CO was 1:1) was introduced. The temperature was raised to 100°C and the reaction pressure was 2 MPa. The reaction was stirred and continued for 5 h to obtain C 6～7 of aldehyde.
[0045] (2) Aldol condensation: Prepare an inorganic alkali solution catalyst, the inorganic alkali in the inorganic alkali solution is sodium hydroxide, and the mass concentration of the inorganic alkali solution is 10%. 6～7 The aldehyde and catalyst were mixed in a T-type micromixer. 6～7The volume ratio of the aldehyde and the catalyst is 1:1, and the mixed solution is then transported to a coil-type microchannel reactor at a flow rate of 3 mL / min for condensation reaction. The length of the coil-type microchannel reactor is 10 m, the inner diameter of the coil-type microchannel reactor is 3 mm, the residence time of the condensation reaction is 1 h, and the temperature of the condensation reaction is 180 ° C. After the reaction is completed, it enters a phase separator to obtain isomeric tridecene aldehyde.
[0046] (3) Hydrogenation and refining: A fixed bed reactor was used for hydrogenation. The feed rate of isomeric tridecene aldehyde was 1.0 g / min, the reaction temperature was 160°C, the reaction pressure was 3 MPa, the nickel catalyst (nickel nitrate hexahydrate) was loaded in an amount of 80 g, and the mass space velocity was 0.5 h -1 The obtained crude isomeric tridecanol is subjected to distillation to obtain isomeric tridecanol.
[0047] Example 3
[0048] The difference from Example 2 is that the tube length of the coil-type microchannel reactor is 50 m, the inner diameter of the tube of the coil-type microchannel reactor is 8 mm, and finally isomeric tridecanol is obtained.
[0049] Example 4
[0050] The difference from Example 2 is that the tube length of the coil-type microchannel reactor is 8 m, the inner diameter of the tube of the coil-type microchannel reactor is 2 mm, and finally isomeric tridecanol is obtained.
[0051] Example 5
[0052] The difference from Example 2 is that the residence time of the condensation reaction is 2 h, the temperature of the condensation reaction is 140° C., and isomeric tridecanol is finally obtained.
[0053] Example 6
[0054] The difference from Example 2 is that the residence time of the condensation reaction is 3 h, the temperature of the condensation reaction is 200° C., and isomeric tridecanol is finally obtained.
[0055] Example 7
[0056] The difference from Example 2 is that the mass concentration of the inorganic alkali solution is 30%, and isomeric tridecanol is finally obtained.
[0057] Example 8
[0058] The difference from Example 2 is that the mass concentration of the inorganic alkali solution is 5%, and isomeric tridecanol is finally obtained.
[0059] Example 9
[0060] The difference from Example 2 is that C 6～7The volume ratio of aldehyde to catalyst is 1:5, and the mixed solution is then transported to a coil-type microchannel reactor at a flow rate of 6 mL / min for condensation reaction to finally obtain isomeric tridecanol.
[0061] Example 10
[0062] The difference from Example 2 is that C 6～7 The volume ratio of aldehyde to catalyst is 1:9, and the mixed solution is then transported to a coil-type microchannel reactor at a flow rate of 10 mL / min for condensation reaction to finally obtain isomeric tridecanol.
[0063] Embodiment 11
[0064] The difference from Example 2 is that the pressure of the hydrogenation reaction is 2.0 MPa, the temperature of the hydrogenation reaction is 160° C., and isomeric tridecanol is finally obtained.
[0065] Example 12
[0066] The difference from Example 2 is that the pressure of the hydrogenation reaction is 5.0 MPa, the temperature of the hydrogenation reaction is 200° C., and isomeric tridecanol is finally obtained.
[0067] Example 13
[0068] The difference from Example 2 is that the feed rate of isomeric tridecene aldehyde is 2 g / min, and the mass space velocity of the hydrogenation reaction is 5 h -1 , and finally obtain isomeric tridecanol.
[0069] Embodiment 14
[0070] The difference from Example 2 is that the feed rate of isomeric tridecene aldehyde is 5 g / min, and the mass space velocity of the hydrogenation reaction is 6 h -1 , and finally obtain isomeric tridecanol.
[0071] Embodiment 15
[0072] The difference from Example 2 is that the temperature of the carbonylation reaction is 120° C., the pressure of the carbonylation reaction is 5 MPa, the time of the carbonylation reaction is 10 h, and finally isomeric tridecanol is obtained.
[0073] Example 16
[0074] The difference from Example 2 is that the temperature of the carbonylation reaction is 85° C., the pressure of the carbonylation reaction is 1 MPa, the time of the carbonylation reaction is 2 h, and finally isomeric tridecanol is obtained.
[0075] Comparative Example 1
[0076] The difference from Example 2 is that a fixed bed reactor is used to replace the coil-type microchannel reactor, and isomeric tridecanol is finally obtained.
[0077] The prepared isomeric tridecanol was analyzed by gas chromatography, and the yield and purity of the isomeric tridecanol are shown in Table 1.
[0078] Table 1
[0079]
[0080] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
[0081] This application adopts C 5～6 The preparation of isomeric tridecanol from Fischer-Tropsch olefins is helpful to enrich the raw material sources for the synthesis of isomeric tridecanol, and C 5～6 The Fischer-Tropsch olefins are more easily available and at a lower cost. The condensation reaction in step S2 is carried out in a microchannel reactor. Compared with traditional kettle reactors and fixed bed reactors, microchannel reactors have significant mass transfer and heat transfer advantages, which can greatly improve the reaction efficiency and selectivity. The use of microchannel reactors helps to promote uniform mixing and contact of materials, so that the condensation catalyst and C 6～7 The mass transfer process between the aldehydes is more efficient, which helps to avoid the formation of by-products caused by local overheating, helps to increase the yield of isomeric tridecene aldehyde, and further helps to increase the yield of the final product isomeric tridecene alcohol.
[0082] The above are only embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims
1. A method for synthesizing isomeric tridecanol, characterized in that: The synthesis method comprises: Step S1: C 5～6 The Fischer-Tropsch olefins react with the synthesis gas under the action of the carbonylation catalyst to obtain C 6～7 Aldehydes; Step S2, the C 6～7 The aldehyde is subjected to condensation reaction under the action of a condensation catalyst to obtain isomeric tridecene aldehyde; Step S3, hydrogenating the isomeric tridecene aldehyde under the action of a hydrogenation catalyst to obtain the isomeric tridecene alcohol; Wherein, the condensation reaction is carried out in a microchannel reactor.
2. The synthesis method according to claim 1, characterized in that In step S2, the microchannel reactor is a coil-type microchannel reactor, the tube length of the coil-type microchannel reactor is 10 to 50 m; and / or the inner diameter of the tube of the coil-type microchannel reactor is 3 to 8 mm; And / or, the condensation reaction is continuously carried out in the microchannel reactor, the C 6～7 The residence time of the aldehyde in the microchannel reactor is 0.1 to 3 hours, preferably 1 to 2 hours; and / or the temperature of the condensation reaction is 90 to 200°C, preferably 140 to 180°C.
3. The synthesis method according to claim 1 or 2, characterized in that In the step S2, the condensation catalyst is an inorganic alkali solution and / or an inorganic solid alkali; Preferably, the inorganic alkaline solution is selected from any one or more of sodium hydroxide solution, potassium hydroxide solution, potassium carbonate solution and sodium carbonate solution; And / or, the inorganic solid base is selected from any one or more of sodium oxide, calcium oxide, magnesium oxide and potassium oxide; Preferably, the condensation catalyst is an inorganic alkali solution, the mass concentration of the inorganic alkali solution is 5% to 30%, preferably 10 to 30%, and the C 6～7 The total feed rate of the aldehyde and the inorganic base solution is 1 to 10 mL / min, preferably 3 to 6 mL / min, and the C 6～7 The volume ratio of the aldehyde to the inorganic alkaline solution is 1:1-5; Preferably, the C 6～7 The aldehyde and the inorganic base solution are mixed in a mixer and then continuously introduced into the microchannel reactor to carry out the condensation reaction.
4. The synthesis method according to any one of claims 1 to 3, characterized in that In step S3, the hydrogenation reaction is carried out in a fixed bed hydrogenation reactor; and / or, the pressure of the hydrogenation reaction is 0.5 to 5.0 MPa, preferably 2.0 to 3.0 MPa; and / or, the temperature of the hydrogenation reaction is 100 to 200° C., preferably 145 to 160° C.; and / or, the feed rate of the isomeric tridecene aldehyde is 0.5 g / min to 5 g / min, preferably 1 to 2 g / min; and / or, the loading amount of the hydrogenation catalyst is 40 to 80 g; and / or, the mass space velocity of the hydrogenation reaction is 0.5 to 5 h -1 .
5. The synthesis method according to any one of claims 1 to 4, characterized in that In step S3, the hydrogenation catalyst is selected from any one or more of a copper-zinc catalyst, a nickel-based catalyst and a palladium-based catalyst; Preferably, the nickel-based catalyst is selected from any one or more of Ni / MgNO3, Ni / diatomaceous earth and Ni / Ga(NO3)2; And / or, the palladium-based catalyst is Pa / Al2O3 and / or Pa / MgNO3.
6. The synthesis method according to any one of claims 1 to 5, characterized in that In the step S1, the temperature of the carbonylation reaction is 85-120° C.; and / or, the pressure of the carbonylation reaction is 1-5 MPa; and / or, the time of the carbonylation reaction is 2-10 h; Preferably, the temperature of the carbonylation reaction is 100-120° C.; and / or, the pressure of the carbonylation reaction is 2-5 MPa; and / or, the time of the carbonylation reaction is 5-10 h.
7. The synthesis method according to any one of claims 1 to 6, characterized in that In step S1, the carbonylation reaction is carried out in a reactor, and the C 5～6 The mass ratio of the Fischer-Tropsch olefin to the carbonylation catalyst is 1:2-5; Preferably, the carbonylation catalyst is a rhodium-based catalyst and / or a cobalt-based catalyst; Further preferably, the rhodium-based catalyst is selected from any one or more of hydrated rhodium trichloride, dicarbonyl rhodium acetylacetonate, tris(sodium triphenylphosphine tris-metasulfonate) carbonyl rhodium chloride and divinyl rhodium acetylacetonate; and / or, the cobalt-based catalyst is selected from any one or more of octacarbonyl dicobalt, cobalt octoate and cobalt chloride hexahydrate.
8. The synthesis method according to any one of claims 1 to 7, characterized in that In parts by weight, the C 5～6 The Fischer-Tropsch olefins include: 25 to 40 parts of normal alkanes, 25 to 60 parts of normal olefins, 10 to 25 parts of isoolefins and 1 to 5 parts of oxygen-containing compounds.
9. The synthesis method according to any one of claims 1 to 8, characterized in that The synthesis method comprises: in the step S2, separating the product of the condensation reaction in a phase separator to obtain the isomeric tridecene aldehyde.
10. The synthesis method according to any one of claims 1 to 9, characterized in that The synthesis method comprises: in the step S3, the product of the hydrogenation reaction is subjected to distillation treatment to obtain the isomeric tridecanol.