Preparation method of mixed high-carbon (C12-C14) isomeric alcohol

Abstract

The invention provides a preparation method of C12-C14 mixed high-carbon isomeric alcohol, which comprises the following steps: reacting C6 aldehyde with C7 aldehyde under the action of a catalyst in a protective atmosphere to obtain a reaction product, and separating to obtain C12-C14 mixed olefine aldehyde; and then carrying out hydrogenation reaction on the C12-C14 mixed olefine aldehyde obtained in the previous step under the action of a hydrogenation catalyst to obtain the C12-C14 mixed isomeric alcohol. The method comprises the following steps: carrying out aldol condensation reaction on C6 aldehyde and C7 aldehyde to generate C12-C14 olefine aldehyde, and carrying out olefine aldehyde hydrogenation to obtain the mixed high-carbon (C12-C14) isomeric alcohol. According to the method, high-carbon olefin is not used as a raw material, so that the problems of relatively large equipment investment, high industrial risk and incapability of large-scale application of a catalyst in an existing synthesis process are solved, and a new thought is provided for preparing high-carbon isomeric odd-number alcohol.

Description

Technical Field

[0001] The invention belongs to the technical field of high carbon isomeric alcohol synthesis, and relates to a method for preparing a mixed high carbon isomeric alcohol of C12-C14, in particular to a method for preparing a mixed high carbon (C12-C14) isomeric alcohol. Background Art

[0002] High carbon isomeric alcohol polyoxyethylene ether synthesized from high carbon isomeric alcohol and ethylene oxide has excellent wettability, permeability and emulsification. In the textile industry and leather industry, it is often used as a component of degreasing agent, detergent, emulsifier and refining agent.

[0003] At present, the industrial methods for producing high-carbon alcohols include natural oil esterification hydrogenation, C10-C16 normal alkane oxidation, Alfort method, and cobalt method high-carbon olefin carbonyl synthesis process. Among them, the natural oil esterification hydrogenation method is limited by resource conditions, and the high-carbon alcohols it produces are mostly normal alcohols; the main product of the normal alkane oxidation method is secondary alcohols with a high carbon number, with a long production process and low product purity. The Alfort method has a complex process and high requirements for equipment. The cobalt method high-carbon olefin carbonyl synthesis process has high reaction pressure, large equipment investment, and high process risk. In addition, although the highly active rhodium catalyst has the advantage of mild process conditions in the field of high-carbon olefin hydroformylation, it cannot solve the problem of rhodium catalyst separation and deactivation, making it impossible for rhodium catalysts to be used on a large scale in the high-carbon olefin hydroformylation industry.

[0004] Therefore, how to design a more suitable synthesis process for high-carbon isomeric alcohols and solve the above-mentioned problems existing in the current synthesis of high-carbon isomeric alcohols has become one of the focuses of widespread attention of many forward-looking researchers in the field. Summary of the invention

[0005] In view of this, the present invention provides a method for preparing a mixed high carbon isomeric alcohol of C12-C14, in particular, a method for preparing a mixed high carbon isomeric alcohol of C12-C14. The synthesis process of mixed high carbon (C12-C14) isomeric alcohol provided by the present invention solves the problems of large equipment investment, high industrial risk and inability of catalyst to be applied to industrialization on a large scale in the existing synthesis process.

[0006] The present invention provides a method for preparing a mixed high-carbon isomeric alcohol of C12-C14, comprising the following steps:

[0007] 1) reacting C6 aldehyde and C7 aldehyde under the action of a catalyst and a protective atmosphere to obtain a reaction product, and then separating to obtain C12-C14 mixed olefin aldehydes;

[0008] 2) The C12-C14 mixed olefins obtained in the above step are subjected to a hydrogenation reaction under the action of a hydrogenation catalyst to obtain C12-C14 mixed isomeric alcohols.

[0009] Preferably, the C6 aldehyde comprises a saturated C6 fatty aldehyde;

[0010] The C7 aldehyde includes a saturated C7 fatty aldehyde;

[0011] The molar ratio of the C6 aldehyde to the C7 aldehyde is 1:(0.03-40).

[0012] Preferably, the C6 aldehyde comprises and / or Wherein, R is an unsubstituted C3 alkyl group;

[0013] The C7 aldehyde includes and / or Wherein, R1 is an unsubstituted C4 alkyl;

[0014] The protective atmosphere includes argon and / or an inert gas.

[0015] Preferably, the catalyst comprises a basic catalyst or an acidic catalyst;

[0016] The alkaline catalyst is one or more of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonium hydroxide solution, an aqueous triethylamine solution or a solid base catalyst;

[0017] The acidic catalyst is one or more of a nitric acid aqueous solution, a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a solid acid catalyst or a strong acid resin catalyst.

[0018] Preferably, the mass concentration of the alkaline catalyst is 0.2% to 50%;

[0019] The mass concentration of the acidic catalyst is 0.2% to 10%;

[0020] The mass ratio of the total mass of the C6 aldehyde and the C7 aldehyde to the mass of the catalyst is 1:(0.1-10).

[0021] Preferably, the pressure of the protective atmosphere is 0.01 to 5 MPa;

[0022] The reaction temperature is 40-200°C;

[0023] The reaction pressure is 0.01-5 MPa.

[0024] Preferably, the reaction is carried out in a reactor or in a fixed bed;

[0025] When the reactor is reacting, the stirring rate of the reactor is 50 to 1000 r / min, and the reaction time is 1 to 24 h;

[0026] When the fixed bed is reacted, the reaction space velocity is 0.3 to 5 h -1 .

[0027] Preferably, the separation method includes normal pressure separation and / or reduced pressure separation.

[0028] Preferably, the hydrogenation reaction is specifically carried out under a hydrogen atmosphere;

[0029] The hydrogenation reaction is carried out using a fixed bed reactor;

[0030] The pressure of the hydrogenation reaction is 0.1-8.0 MPa;

[0031] The temperature of the hydrogenation reaction is 60 to 360°C;

[0032] The space velocity of the hydrogenation reaction is 0.1 to 5 h -1 .

[0033] Preferably, the C12-C14 mixed high carbon isomeric alcohol includes C13 isomeric alcohol, C12 isomeric alcohol and C14 isomeric alcohol;

[0034] The mass content of the C13 isomeric alcohol is 0.1% to 85%.

[0035] The present invention provides a method for preparing a mixed high-carbon isomeric alcohol of C12-C14, comprising the following steps: first, reacting C6 aldehyde and C7 aldehyde under the action of a catalyst and a protective atmosphere to obtain a reaction product, and obtaining C12-C14 mixed olefinic aldehyde after separation; and then subjecting the C12-C14 mixed olefinic aldehyde obtained in the above steps to a hydrogenation reaction under the action of a hydrogenation catalyst to obtain a mixed isomeric alcohol of C12-C14. Compared with the prior art, the present invention particularly designs a new process and a new route for preparing a mixed high-carbon isomeric alcohol of C12-C14, wherein C6 aldehyde and C7 aldehyde are subjected to an aldol condensation reaction to generate C12-C14 olefinic aldehyde, and then a mixed high-carbon (C12-C14) isomeric alcohol is obtained by hydrogenating the olefinic aldehyde. The present invention does not use high-carbon olefins as raw materials, thereby avoiding the problems of large equipment investment, high industrial risk and inability to apply catalysts on a large scale in the existing synthesis process, and provides a new idea for preparing high-carbon isomeric odd-number alcohols.

[0036] The experimental results show that the content of isomeric C13 alcohol in the mixed high-carbon (C12-C14) isomeric alcohol prepared by the present invention is 0-85%. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1The gas chromatogram of the intermediate product mixed olefin aldehyde (C12-C14) prepared by the present invention;

[0038] Figure 2 This is a gas chromatogram of the hydrogenated product mixed high-carbon (C12-C14) isomeric alcohol prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0039] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0040] All raw materials of the present invention have no particular limitation on their sources, and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0041] There is no particular limitation on the purity of all raw materials in the present invention. The present invention preferably uses analytically pure raw materials or raw materials of conventional purity used in the field of preparation of high-carbon isomerized alcohols.

[0042] All noun expressions, abbreviations and trademarks in the present invention are conventional noun expressions, abbreviations and trademarks in the field. Each noun expression, abbreviation and trademark is clear and unambiguous in its relevant application field, and those skilled in the art can clearly, accurately and uniquely understand it based on the noun expressions, abbreviations and trademarks.

[0043] The present invention provides a method for preparing a mixed high-carbon isomeric alcohol of C12-C14, comprising the following steps:

[0044] 1) reacting C6 aldehyde and C7 aldehyde under the action of a catalyst and a protective atmosphere to obtain a reaction product, and then separating to obtain C12-C14 mixed olefin aldehydes;

[0045] 2) The C12-C14 mixed olefins obtained in the above step are subjected to a hydrogenation reaction under the action of a hydrogenation catalyst to obtain C12-C14 mixed isomeric alcohols.

[0046] In the present invention, the isomeric alcohol preferably refers to a branched alcohol, more specifically a branched saturated alcohol.

[0047] The invention firstly reacts C6 aldehyde and C7 aldehyde under the action of a catalyst and a protective atmosphere to obtain a reaction product, and then obtains C12-C14 mixed olefin aldehyde after separation.

[0048] In the present invention, the C6 aldehyde preferably includes saturated C6 aliphatic aldehyde, and more preferably includes C6 straight-chain aldehyde and / or C6 branched-chain aldehyde.

[0049] In the present invention, the C7 aldehyde preferably includes saturated C7 aliphatic aldehyde, and more preferably includes C7 straight-chain aldehyde and / or C7 branched-chain aldehyde.

[0050] In the present invention, the molar ratio of the C6 aldehyde to the C7 aldehyde is preferably 1:(0.03-40), more preferably 1:(1-30), and even more preferably 1:(10-20).

[0051] In the present invention, the C6 aldehyde preferably includes:

[0052] and / or Wherein, R is an unsubstituted C3 alkyl group.

[0053] Furthermore, the C6 aldehyde preferably includes one or more of n-hexanal, 3-methylpentanal, 4-methylpentanal and 3,3-dimethylbutanal.

[0054] In the present invention, the C7 aldehyde preferably includes:

[0055] and / or Wherein, R1 is an unsubstituted C4 alkyl group.

[0056] Further, the C7 aldehyde preferably includes one or more of n-heptylaldehyde, 5-methylhexanal, 4-methylhexanal, 3-methylhexanal, 4,4-dimethylvaleraldehyde, 3,3-dimethylvaleraldehyde, 3,4-dimethylvaleraldehyde and 3-ethylvaleraldehyde.

[0057] In the present invention, the protective atmosphere preferably includes argon and / or an inert gas, more preferably argon or an inert gas.

[0058] In the present invention, the catalyst preferably includes a basic catalyst or an acidic catalyst.

[0059] In the present invention, the alkaline catalyst is preferably one or more of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonium hydroxide solution, an aqueous triethylamine solution or a solid base catalyst, more preferably an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonium hydroxide solution, an aqueous triethylamine solution or a solid base catalyst.

[0060] In the present invention, the acidic catalyst is preferably one or more of an aqueous nitric acid solution, an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, a solid acid catalyst or a strong acid resin catalyst, and more preferably an aqueous nitric acid solution, an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, a solid acid catalyst or a strong acid resin catalyst.

[0061] In the present invention, the mass concentration of the alkaline catalyst is preferably 0.2% to 50%, more preferably 10% to 40%, and more preferably 20% to 30%.

[0062] In the present invention, the mass concentration of the acidic catalyst is 0.2% to 10%, more preferably 1% to 9%, more preferably 3% to 7%, more preferably 4% to 6%.

[0063] In the present invention, the mass ratio of the total mass of the C6 aldehyde and the C7 aldehyde to the mass of the catalyst is preferably 1:(0.1-10), more preferably 1:(1-8), and more preferably 1:(3-6).

[0064] In the present invention, the pressure of the protective atmosphere is preferably 0.01 to 5 MPa, more preferably 0.1 to 4 MPa, and even more preferably 1 to 3 MPa.

[0065] In the present invention, the reaction temperature is preferably 40 to 200°C, more preferably 70 to 170°C, and even more preferably 100 to 140°C.

[0066] In the present invention, the reaction pressure is preferably 0.01 to 5 MPa, more preferably 0.1 to 4 MPa, and even more preferably 1 to 3 MPa.

[0067] In the present invention, the reaction is preferably carried out in a reactor or in a fixed bed.

[0068] In the present invention, when the reaction kettle is reacting, the stirring rate of the reaction kettle is preferably 50 to 1000 r / min, more preferably 250 to 800 r / min, more preferably 450 to 600 r / min. The reaction time is preferably 1 to 24 h, more preferably 5 to 20 h, more preferably 10 to 15 h.

[0069] The stirring rate of the reactor is preferably 50 to 1000 r / min, more preferably 250 to 800 r / min, and more preferably 450 to 600 r / min.

[0070] In the present invention, when the fixed bed is reacted, the reaction space velocity is preferably 0.3 to 5 h -1 , more preferably 1 to 4 hours -1 , more preferably 2 to 3 hours -1 .

[0071] In the present invention, the separation method preferably includes normal pressure separation and / or reduced pressure separation.

[0072] Finally, the present invention subjects the C12-C14 mixed olefinic aldehydes obtained in the above steps to a hydrogenation reaction under the action of a hydrogenation catalyst to obtain C12-C14 mixed isomeric alcohols.

[0073] In the present invention, the hydrogenation reaction is preferably carried out under a hydrogen atmosphere.

[0074] In the present invention, the hydrogenation reaction is preferably carried out in a fixed bed reactor.

[0075] In the present invention, the hydrogenation catalyst preferably includes one or more of a Pt-based catalyst, a Pd-based catalyst and a Ni-based catalyst, and more preferably a Pt-based catalyst, a Pd-based catalyst or a Ni-based catalyst. Specifically, it can be 0.5% Pt-Al2O3, 0.5% Pt-C, 2% Pt-Al2O3, 0.5% Pd-C, 25% Ni-75% Al2O3, 25% Ni-75% SiO2, 25% Ni-15% Ti-60% Al2O3, 20% Ni-5% Cu-14% Ti-61% Al2O3 or a Raney nickel catalyst.

[0076] In the present invention, the pressure of the hydrogenation reaction is preferably 0.1 to 8.0 MPa, more preferably 0.5 to 7.0 MPa, more preferably 1.0 to 6.0 MPa, and more preferably 2.0 to 5.0 MPa.

[0077] In the present invention, the temperature of the hydrogenation reaction is preferably 60 to 360°C, more preferably 100 to 300°C, and more preferably 150 to 250°C.

[0078] In the present invention, the space velocity of the hydrogenation reaction is preferably 0.1 to 5 h -1 , more preferably 0.5 to 2.5 h -1 , more preferably 1 to 2 hours -1 .

[0079] In the present invention, the C12-C14 mixed high-carbon isomeric alcohol preferably includes C13 isomeric alcohol, C12 isomeric alcohol and C14 isomeric alcohol.

[0080] In the present invention, the mass content of the C13 isomeric alcohol is preferably 0.1% to 85%, more preferably 1% to 75%, more preferably 10% to 65%, more preferably 20% to 55%.

[0081] The present invention is to complete and refine the overall technical solution, better ensure the structure and composition of C12-C14 mixed high-carbon isomerized alcohol, and further improve the stability and efficiency of the preparation method. The preparation method of the C12-C14 mixed high-carbon isomerized alcohol can specifically include the following contents:

[0082] A method for preparing mixed high-carbon (C12-C14) isomeric alcohols, wherein the content of isomeric C13 alcohols in the mixed high-carbon (C12-C14) isomeric alcohols is 0-85%, and the rest is isomeric C12 alcohols and isomeric C14 alcohols.

[0083] The method for preparing mixed high-carbon (C12-C14) isomeric alcohols provided by the present invention comprises the following steps:

[0084] 1) C6 aldehyde and C7 aldehyde react in a tank reactor and / or a fixed bed reactor in the presence of a catalyst to generate mixed high carbon (C12-C14) olefinic aldehydes;

[0085] 2) Separating mixed high-carbon (C12-C14) olefinic aldehydes;

[0086] 3) The separated mixed high-carbon (C12-C14) olefinic aldehydes are hydrogenated to obtain mixed high-carbon (C12-C14) isomeric alcohols.

[0087] Specifically, the C6 aldehyde and C7 aldehyde are saturated C6 fatty aldehyde and saturated C7 fatty aldehyde.

[0088] Specifically, the catalyst in step 1) is a basic catalyst or an acidic catalyst.

[0089] Specifically, the alkaline catalyst in step 1) is one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonium hydroxide aqueous solution, triethylamine aqueous solution or solid base catalyst.

[0090] Specifically, the acidic catalyst in step 1) is one or more of nitric acid aqueous solution, hydrochloric acid aqueous solution, sulfuric acid aqueous solution, solid acid catalyst or strong acid resin catalyst.

[0091] Specifically, the mass content of the solute in the sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonium hydroxide aqueous solution, triethylamine aqueous solution, nitric acid aqueous solution, hydrochloric acid aqueous solution, and sulfuric acid aqueous solution is 0.2-50%.

[0092] Specifically, in the method for preparing mixed high-carbon (C12-C14) isomeric alcohols, the reaction temperature in step 1) is 40-200°C.

[0093] Specifically, the method for preparing mixed high-carbon (C12-C14) isomeric alcohols is characterized in that the reaction pressure in step 1) is 0-5.0 MPa.

[0094] Specifically, in the method for preparing mixed high-carbon (C12-C14) isomeric alcohols, the molar ratio of C6 aldehyde to C7 aldehyde in step 1) is C6 aldehyde:C7 aldehyde=1:0.03-40.

[0095] Specifically, in the method for preparing mixed high-carbon (C12-C14) isomeric alcohols, in step 1), when C6 aldehyde and C7 aldehyde react to generate mixed high-carbon (C12-C14) olefinic aldehydes using a reactor, the total mass of C6 aldehyde and C7 aldehyde: catalyst solution (mass ratio) is 1:0.1-10, the stirring rate is 50-1000 r / min, and the reaction time is 1-24 h.

[0096] Specifically, in the method for preparing mixed high-carbon (C12-C14) isomeric alcohols, in step 1), C6 aldehyde and C7 aldehyde are reacted to generate mixed high-carbon (C12-C14) olefinic aldehydes. When a fixed bed reactor is used, the reaction space velocity is 0.3-5h -1 .

[0097] Specifically, the method for preparing mixed high-carbon (C12-C14) isomeric alcohols is characterized in that the reaction pressure in step 3) is 0-8.0 MPa and the reaction temperature is 60-360°C.

[0098] Among them, a method for preparing a mixed high-carbon (C12-C14) isomeric alcohol comprises the following steps:

[0099] A: If the mixed high-carbon (C12-C14) alkenyl aldehydes in step 1) are synthesized using a reaction kettle reactor, the method for preparing the mixed high-carbon (C12-C14) isomeric alcohols is as follows:

[0100] 1) A certain pressure of nitrogen is charged into the reactor, and the nitrogen is replaced 3-5 times, and then a certain amount of catalyst is added into the reactor, and finally C6 aldehyde and C7 aldehyde are introduced into the reactor. Nitrogen is charged, the pressure required for the reaction is maintained, stirring is started, and the mixed olefin aldehyde (C12-C14) is obtained by heating the reaction.

[0101] 2) Separate the mixed olefins (C12-C14).

[0102] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated to generate mixed high carbon (C12-C14) isomeric alcohols.

[0103] Furthermore, in the above technical solution, in step 1), the catalyst is a basic catalyst or an acidic catalyst. The preferred catalyst is one or more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a triethylamine aqueous solution, and an ammonium hydroxide aqueous solution.

[0104] Furthermore, in the above technical solution, in step 1), the reaction temperature is 40-200°C, and the preferred reaction temperature is 120-180°C.

[0105] Furthermore, in the above technical solution, in step 1), the reaction pressure is 0-5.0 MPa, and the preferred reaction pressure is 0-2.0 MPa.

[0106] Furthermore, in the above technical solution, in step 1), the molar ratio of C6 aldehyde to C7 is 1:0.03-40, preferably 1:0.3-3, and most preferably 1:0.5-1.5.

[0107] Furthermore, in the above technical solution, in step 1), the total mass of C6 aldehyde and C7 aldehyde: catalyst solution (mass ratio) is 1:0.1-10, preferably 1:0.3-2, and most preferably 1:0.5-1.2.

[0108] Furthermore, in the above technical solution, the mass content of the solute in the catalyst solution in step 1) is 0.2-50%, preferably 0.5-25%, more preferably 1-10%, and most preferably 1.5-5%.

[0109] Furthermore, in the above technical solution, in step 1), the stirring rate is 50-1000 r / min, preferably 150-600 r / min, and more preferably 200-350 r / min.

[0110] Furthermore, in the above technical solution, in step 1), the reaction time is 1-24 h, preferably 3-16 h, and most preferably 5-10 h.

[0111] Furthermore, in the above technical solution, in step 3), the reaction pressure is 0-8.0 MPa, preferably 2.0-6.0 MPa, and most preferably 3.0-4.0 MPa.

[0112] Furthermore, in the above technical solution, in step 3), the reaction temperature is 60-360°C, preferably 110-300°C, and most preferably 150-210°C.

[0113] A method for preparing a mixed high-carbon (C12-C14) isomeric alcohol comprises the following steps:

[0114] B: If the mixed high-carbon (C12-C14) olefinic aldehydes in step 1) are synthesized using a fixed bed reactor, the method for preparing the mixed high-carbon (C12-C14) isomeric alcohols is as follows:

[0115] 1) The solid catalyst is loaded into a fixed bed reactor, and then a certain pressure of nitrogen is filled into the reactor, and the reactor is replaced 3 to 5 times, and then nitrogen is filled again to maintain the pressure required for the reaction. Finally, C6 aldehyde and C7 aldehyde are introduced into the reactor, and the mixed olefin aldehyde (C12 to C14) is obtained by heating the reaction.

[0116] 2) Separate the mixed olefins (C12-C14).

[0117] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated to generate mixed high-carbon (C12-C14) isomeric alcohols.

[0118] Furthermore, in the above technical solution, in step 1), the catalyst is one or more of a solid base catalyst, a solid acid catalyst and a strong acid resin catalyst, preferably one or more of a solid phosphoric acid catalyst and a strong acid resin catalyst.

[0119] Furthermore, in the above technical solution, in step 1), the reaction space velocity is 0.3-5h -1 , preferably 0.5-2.5h -1 , preferably 0.5-1.0h -1 .

[0120] Furthermore, in the above technical solution, in step 1), the reaction temperature is 40-200°C, and the preferred reaction temperature is 120-180°C.

[0121] Furthermore, in the above technical solution, in step 1), the reaction pressure is 0-5.0 MPa, and the preferred reaction pressure is 0-2.0 MPa.

[0122] Furthermore, in the above technical solution, in step 1), the molar ratio of C6 aldehyde to C7 is 1:0.03-40, preferably 1:0.3-3, and preferably 1:0.5-1.5.

[0123] Furthermore, in the above technical solution, in step 3), the reaction pressure is 0-8.0 MPa, preferably 2.0-6.0 MPa, and most preferably 3.0-4.0 MPa.

[0124] Furthermore, in the above technical solution, in step 3), the reaction temperature is 60-360°C, preferably 110-300°C, and most preferably 150-210°C.

[0125] The above content of the present invention provides a method for preparing a mixed high-carbon (C12-C14) isomeric alcohol. The present invention generates C12-C14 olefins by aldol condensation reaction of C6 aldehyde and C7 aldehyde, and then obtains a mixed high-carbon (C12-C14) isomeric alcohol by olefin hydrogenation. The present invention does not use high-carbon olefins as raw materials, avoids the problems of large equipment investment, high industrial risk and inability to apply catalysts on a large scale in the existing synthesis process, and provides a new idea for preparing high-carbon isomeric odd-number alcohols.

[0126] The experimental results show that the content of isomeric C13 alcohol in the mixed high-carbon (C12-C14) isomeric alcohol prepared by the present invention is 0-85%.

[0127] To further illustrate the present invention, a method for preparing a mixed high-carbon (C12-C14) isomeric alcohol provided by the present invention is described in detail below in conjunction with examples. However, it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and detailed implementation methods and specific operating processes are given only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention, and the protection scope of the present invention is not limited to the following examples.

[0128] Example 1

[0129] A method for preparing a mixed high-carbon (C12-C14) isomeric alcohol comprises the following steps:

[0130] 1)① Mix 15g C6 aldehyde (a mixture of 3-methylpentanal, 4-methylpentanal and 2,3-dimethylbutanal) and 17g C7 aldehyde (n-heptanal) and add them to a 100ml reactor, then add 32g 3wt% NaOH solution. ② Fill the reactor with nitrogen, maintain the pressure at about 0.5MPa, replace 3-5 times, then maintain the pressure at 0.1MPa, start stirring, the stirring rate is 300r / min, start heating to 140℃, and react for 10h. ③ After the reaction is completed, wait for the system to cool to room temperature, take the reaction product for chromatographic analysis, the conversion rate of mixed aldehydes is 90.0%, and the selectivity of mixed olefin aldehydes (C12~C14) is 97.9%.

[0131] 2) Mixed olefins (C12-C14) are obtained by separation.

[0132] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated over a nickel-based (25% Ni-15% Ti-60% Al2O3) hydrogenation catalyst to prepare mixed high-carbon (C12-C14) isomeric alcohols, at a reaction temperature of 190° C. and a pressure of 3.0 MPa. The conversion rate of the mixed olefin aldehydes (C12-C14) is 98.2%, the selectivity of the mixed high-carbon (C12-C14) isomeric alcohols is 98.7%, and the content of C13 isomeric alcohol in the product mixed high-carbon (C12-C14) isomeric alcohols is 65.31%.

[0133] See also Figure 1 , Figure 1 This is a gas chromatogram of the intermediate product mixed olefin aldehydes (C12-C14) prepared in the present invention.

[0134] See also Figure 2 , Figure 2 This is a gas chromatogram of the hydrogenated product mixed high-carbon (C12-C14) isomeric alcohol prepared in Example 1 of the present invention.

[0135] Example 2

[0136] Compared with Example 1, the reaction temperature of step 1) is adjusted.

[0137] A method for preparing a mixed high-carbon (C12-C14) isomeric alcohol comprises the following steps:

[0138] 1)① 15g C6 aldehyde (mixture of 3-methylpentanal, 4-methylpentanal and 2,3-dimethylbutanal) and 17g C7 aldehyde (n-heptanal) were mixed and added to a 100ml reactor, followed by 32g 3wt% NaOH solution. ② Nitrogen was charged into the reactor, the pressure was maintained at about 0.5MPa, and the pressure was replaced 3-5 times, and then the pressure was maintained at 0.1MPa, stirring was started, the stirring rate was 300r / min, the temperature was raised to 180℃, and the reaction was carried out for 10h. ③ After the reaction was completed, the system was cooled to room temperature, and the reaction product was taken for chromatographic analysis. The conversion rate of the mixed aldehyde was 95.0%, and the selectivity of the mixed olefin aldehyde (C12-C14) was 97.1%.

[0139] 2) Mixed olefins (C12-C14) are obtained by separation.

[0140] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated over a nickel-based (25% Ni-15% Ti-60% Al2O3) hydrogenation catalyst to prepare mixed high-carbon (C12-C14) isomeric alcohols, at a reaction temperature of 190° C. and a pressure of 3.0 MPa. The conversion rate of the mixed olefin aldehydes (C12-C14) isomeric alcohols is 98.6%, the selectivity of the mixed high-carbon (C12-C14) isomeric alcohols is 98.5%, and the content of C13 isomeric alcohols in the mixed high-carbon (C12-C14) isomeric alcohols is 65.16%.

[0141] Example 3

[0142] Compared with Example 1, the amount of NaOH solution in step 1) is adjusted.

[0143] A method for preparing a mixed high-carbon (C12-C14) isomeric alcohol comprises the following steps:

[0144] 1)① Mix 15g C6 aldehyde (a mixture of 3-methylpentanal, 4-methylpentanal and 2,3-dimethylbutanal) and 17g C7 aldehyde (n-heptanal) and add them to a 100ml reactor, then add 16g 3wt% NaOH solution. ② Fill the reactor with nitrogen, maintain the pressure at about 0.5MPa, replace 3-5 times, then maintain the pressure at 0.1MPa, start stirring, the stirring rate is 300r / min, start heating to 140℃, and react for 10h. ③ After the reaction is completed, wait for the system to cool to room temperature, take the reaction product for chromatographic analysis, the conversion rate of mixed aldehydes is 65.6%, and the selectivity of mixed olefin aldehydes (C12~C14) is 96.9%.

[0145] 2) Mixed olefins (C12-C14) are obtained by separation.

[0146] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated over a nickel-based (25% Ni-15% Ti-60% Al2O3) hydrogenation catalyst to prepare mixed high-carbon (C12-C14) isomeric alcohols, at a reaction temperature of 190° C. and a pressure of 3.0 MPa. The conversion rate of the mixed olefin aldehydes (C12-C14) is 98.4%, the selectivity of the mixed high-carbon (C12-C14) isomeric alcohols is 98.7%, and the content of C13 isomeric alcohol in the product mixed high-carbon (C12-C14) isomeric alcohols is 65.25%.

[0147] Example 4

[0148] Compared with Example 1, the reaction time in step 1) is adjusted.

[0149] A method for preparing a mixed high-carbon (C12-C14) isomeric alcohol comprises the following steps:

[0150] 1)① Mix 15g C6 aldehyde (a mixture of 3-methylpentanal, 4-methylpentanal and 2,3-dimethylbutanal) and 17g C7 aldehyde (n-heptanal) and add them to a 100ml reactor, then add 32g 3wt% NaOH solution. ② Fill the reactor with nitrogen, maintain the pressure at about 0.5MPa, replace 3-5 times, then maintain the pressure at 0.1MPa, start stirring, the stirring rate is 300r / min, start heating to 140℃, and react for 16h. ③ After the reaction is completed, wait for the system to cool to room temperature, take the reaction product for chromatographic analysis, the conversion rate of mixed aldehydes is 95.3%, and the selectivity of mixed olefin aldehydes (C12~C14) is 97.8%.

[0151] 2) Mixed olefins (C12-C14) are obtained by separation.

[0152] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated over a nickel-based (25% Ni-15% Ti-60% Al2O3) hydrogenation catalyst to prepare mixed high-carbon (C12-C14) isomeric alcohols, at a reaction temperature of 190° C. and a pressure of 3.0 MPa. The conversion rate of the mixed olefin aldehydes (C12-C14) is 98.7%, the selectivity of the mixed high-carbon (C12-C14) isomeric alcohols is 98.8%, and the content of C13 isomeric alcohol in the product mixed high-carbon (C12-C14) isomeric alcohols is 65.17%.

[0153] Example 5

[0154] Compared with Example 1, the ratio of C6 aldehyde to C7 aldehyde in step 1) is adjusted.

[0155] A method for preparing a mixed high-carbon (C12-C14) isomeric alcohol comprises the following steps:

[0156] 1)① Mix 10g C6 aldehyde (a mixture of 3-methylpentanal, 4-methylpentanal and 2,3-dimethylbutanal) and 22g C7 aldehyde (n-heptanal) and add them to a 100ml reactor, then add 32g 3wt% NaOH solution. ② Fill the reactor with nitrogen, maintain the pressure at about 0.5MPa, replace 3-5 times, then maintain the pressure at 0.1MPa, start stirring, the stirring rate is 300r / min, start heating to 140℃, and react for 10h. ③ After the reaction is completed, wait for the system to cool to room temperature, take the reaction product for chromatographic analysis, the conversion rate of mixed aldehydes is 89.3%, and the selectivity of mixed olefin aldehydes (C12~C14) is 98.2%.

[0157] 2) Mixed olefins (C12-C14) are obtained by separation.

[0158] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated over a nickel-based (25% Ni-15% Ti-60% Al2O3) hydrogenation catalyst to prepare mixed high-carbon (C12-C14) isomeric alcohols, at a reaction temperature of 190° C. and a pressure of 3.0 MPa. The conversion rate of the mixed olefin aldehydes (C12-C14) is 98.5%, the selectivity of the mixed high-carbon (C12-C14) isomeric alcohols is 98.3%, and the content of C13 isomeric alcohol in the product mixed high-carbon (C12-C14) isomeric alcohols is 44.63%.

[0159] Example 6

[0160] Compared with Example 1, the ratio of C6 aldehyde to C7 aldehyde in step 1) is adjusted.

[0161] A method for preparing a mixed high-carbon (C12-C14) isomeric alcohol comprises the following steps:

[0162] 1)① Mix 22g of C6 aldehyde (a mixture of 3-methylpentanal, 4-methylpentanal and 2,3-dimethylbutanal) and 10g of C7 aldehyde (n-heptanal) and add them to a 100ml reactor, then add 32g of 3wt% NaOH solution. ② Fill the reactor with nitrogen, maintain the pressure at about 0.5MPa, replace 3-5 times, then maintain the pressure at 0.1MPa, start stirring, the stirring rate is 300r / min, start heating to 140℃, and react for 10h. ③ After the reaction is completed, wait for the system to cool to room temperature, take the reaction product for chromatographic analysis, the conversion rate of mixed aldehydes is 91.0%, and the selectivity of mixed olefin aldehydes (C12~C14) is 97.6%.

[0163] 2) Mixed olefins (C12-C14) are obtained by separation.

[0164] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated over a nickel-based (25% Ni-15% Ti-60% Al2O3) hydrogenation catalyst to prepare mixed high-carbon (C12-C14) isomeric alcohols, at a reaction temperature of 190° C. and a pressure of 3.0 MPa. The conversion rate of the mixed olefin aldehydes (C12-C14) is 98.6%, the selectivity of the mixed high-carbon (C12-C14) isomeric alcohols is 98.3%, and the content of C13 isomeric alcohol in the product mixed high-carbon (C12-C14) isomeric alcohols is 46.55%.

[0165] Example 7

[0166] Compared with Example 1, the reaction time in step 1) is adjusted.

[0167] 1)① Mix 15g C6 aldehyde (a mixture of 3-methylpentanal, 4-methylpentanal and 2,3-dimethylbutanal) and 17g C7 aldehyde (n-heptanal) and add them to a 100ml reactor, then add 32g 3wt% NaOH solution. ② Fill the reactor with nitrogen, maintain the pressure at about 0.5MPa, replace 3-5 times, then maintain the pressure at 0.1MPa, start stirring, the stirring rate is 300r / min, start heating to 140℃, and react for 12h. ③ After the reaction is completed, wait for the system to cool to room temperature, take the reaction product for chromatographic analysis, the conversion rate of mixed aldehydes is 92.3%, and the selectivity of mixed olefin aldehydes (C12~C14) is 98.3%.

[0168] 2) Mixed olefins (C12-C14) are obtained by separation.

[0169] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated over a nickel-based (25% Ni-15% Ti-60% Al2O3) hydrogenation catalyst to prepare mixed high-carbon (C12-C14) isomeric alcohols, at a reaction temperature of 190° C. and a pressure of 3.0 MPa. The conversion rate of the mixed olefin aldehydes (C12-C14) is 98.8%, the selectivity of the mixed high-carbon (C12-C14) isomeric alcohols is 98.5%, and the content of C13 isomeric alcohols in the mixed high-carbon (C12-C14) isomeric alcohols is 65.09%.

[0170] Example 8

[0171] Compared with Example 1, the reaction temperature of step 3) is adjusted.

[0172] 1) ① Mix 15g C6 aldehyde (a mixture of 3-methylpentanal, 4-methylpentanal and 2,3-dimethylbutanal) and 17g C7 aldehyde (n-heptanal) and add them to a 100ml reactor, then add 32g 3wt% NaOH solution. ② Fill the reactor with nitrogen, maintain the pressure at about 0.5MPa, replace 3-5 times, then maintain the pressure at 0.1MPa, start stirring, the stirring rate is 300r / min, start heating to 140℃, and react for 10h. ③ After the reaction is completed, wait for the system to cool to room temperature, take the reaction product for chromatographic analysis, the conversion rate of the mixed aldehyde is 90.0%, and the selectivity is 97.9%.

[0173] 2) Mixed olefins (C12-C14) are obtained by separation.

[0174] 3) The separated mixed olefin aldehydes (C12-C14) are hydrogenated over a nickel-based (25% Ni-15% Ti-60% Al2O3) hydrogenation catalyst to prepare mixed high-carbon (C12-C14) isomeric alcohols, at a reaction temperature of 180° C. and a pressure of 3.0 MPa. The conversion rate of the mixed olefin aldehydes (C12-C14) is 98.3%, the selectivity of the mixed high-carbon (C12-C14) isomeric alcohols is 97.6%, and the content of C13 isomeric alcohol in the product mixed high-carbon (C12-C14) isomeric alcohols is 65.27%.

[0175] The above is a detailed introduction to the preparation method of a mixed high-carbon (C12-C14) isomeric alcohol provided by the present invention. The principle and implementation method of the present invention are described in detail using specific examples. The description of the above embodiments is only used to help understand the method and its core idea of ​​the present invention, including the best mode, and also enables any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements that are not different from the text of the claims, or if they include equivalent structural elements that are not substantially different from the text of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A method for preparing a mixed high carbon isomerized alcohol of C12 to C14, characterized in that: The following steps are involved: 1) reacting C6 aldehyde and C7 aldehyde under the action of a catalyst and a protective atmosphere to obtain a reaction product, and then separating to obtain C12-C14 mixed olefin aldehydes; 2) The C12-C14 mixed olefins obtained in the above step are subjected to a hydrogenation reaction under the action of a hydrogenation catalyst to obtain C12-C14 mixed isomeric alcohols.

2. The preparation method according to claim 1, characterized in that: The C6 aldehyde includes a saturated C6 fatty aldehyde; The C7 aldehyde includes a saturated C7 fatty aldehyde; The molar ratio of the C6 aldehyde to the C7 aldehyde is 1:(0.03-40).

3. The preparation method according to claim 1, characterized in that: The C6 aldehyde includes Wherein, R is an unsubstituted C3 alkyl group; The C7 aldehyde includes Wherein, R1 is an unsubstituted C4 alkyl; The protective atmosphere includes argon and / or an inert gas.

4. The preparation method according to claim 1, characterized in that: The catalyst includes a basic catalyst or an acidic catalyst; The alkaline catalyst is one or more of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous ammonium hydroxide solution, an aqueous triethylamine solution or a solid base catalyst; The acidic catalyst is one or more of a nitric acid aqueous solution, a hydrochloric acid aqueous solution, a sulfuric acid aqueous solution, a solid acid catalyst or a strong acid resin catalyst.

5. The preparation method according to claim 4, characterized in that: The mass concentration of the alkaline catalyst is 0.2% to 50%; The mass concentration of the acidic catalyst is 0.2% to 10%; The mass ratio of the total mass of the C6 aldehyde and the C7 aldehyde to the mass of the catalyst is 1:(0.1-10).

6. The preparation method according to claim 1, characterized in that: The pressure of the protective atmosphere is 0.01-5 MPa; The reaction temperature is 40-200°C; The reaction pressure is 0.01-5 MPa.

7. The preparation method according to claim 1, characterized in that: The reaction is specifically carried out in a reactor or in a fixed bed; When the reactor is reacting, the stirring rate of the reactor is 50 to 1000 r / min, and the reaction time is 1 to 24 h; When the fixed bed is reacted, the reaction space velocity is 0.3 to 5 h -1 .

8. The preparation method according to claim 1, characterized in that: The hydrogenation reaction is specifically carried out under a hydrogen atmosphere; The hydrogenation reaction is carried out in a fixed bed reactor.

9. The preparation method according to claim 1, characterized in that: The pressure of the hydrogenation reaction is 0.1-8.0 MPa; The temperature of the hydrogenation reaction is 60 to 360°C; The space velocity of the hydrogenation reaction is 0.1 to 5 h -1 .

10. The preparation method according to claim 1, characterized in that: The separation method includes normal pressure separation and / or reduced pressure separation; The C12-C14 mixed high carbon isomeric alcohol includes C13 isomeric alcohol, C12 isomeric alcohol and C14 isomeric alcohol; The mass content of the C13 isomeric alcohol is 0.1% to 85%.

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