CN115974649B - Method for producing sec-octyl alcohol - Google Patents
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Abstract
The present invention provides a method for producing sec-octanol. The method for producing the sec-octanol comprises the following steps: and (3) carrying out hydrogenation reaction on the secondary octanone in the presence of a hydrogenation catalyst and a catalyst auxiliary agent, wherein the catalyst auxiliary agent comprises acyclic carboxylic anhydride and/or cyclic carboxylic anhydride. The preparation method of the invention can obtain the sec-octyl alcohol with high conversion rate in a short time, has simple process, convenient operation and mild reaction condition, and is particularly suitable for industrial large-scale and high-efficiency production. In addition, the preparation method is also suitable for a crude sec-octanol system, can solve the problem of difficult separation of sec-octanol and sec-octanone, and simplifies the process for extracting refined sec-octanol by rectifying the crude sec-octanol.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a method for manufacturing sec-octyl alcohol.
Background
Fatty alcohols and fatty ketones are important chemical raw materials, and in industrial production, hydrogenation of ketones to alcohols is the most commonly used method.
The sec-octanol is an important chemical raw material and organic solvent, and can be used as a wetting agent, a spice, a plasticizer and a pesticide emulsifier, and can also be used as a raw material for producing high-grade lubricating oil additives. The secondary octanol mainly comes from a byproduct of the preparation of sebacic acid by castor oil hydrolysis, and the content of the crude secondary octanol is only about 80 percent, and the crude secondary octanol contains 15 to 20 percent of 2-octanone, so that the application of the crude secondary octanol is limited. There are generally two methods for preparing high purity sec-octanol from industrial sec-octanol: firstly, washing with NaHSO 3 solution by a chemical method, separating 2-octanone, and simultaneously obtaining sec-octanol and 2-octanone; another method is a hydrogenation method; the 2-octanone in the sec-octanol is hydrogenated and reduced to the sec-octanol. The chemical treatment cannot achieve the expected result, the operation is complex, and the three wastes are more. The hydrogenation reduction method has high product yield, is a clean process, and is more suitable for industrialization.
In the current report of patent literature for preparing sec-octanol by sec-octanone hydrogenation, chinese patent application CN1974514A discloses a research on preparing sec-octanol by sec-octanone hydrogenation on a magnetic reaction fixed bed by using a catalyst with ferromagnetism, wherein the preparation pressure is 0.1-1.5 MPa, the temperature is 70-120 ℃, the magnetic field strength is 10-30 KA/m, ethanol is used as a solvent in the process, and when Raney nickel is used as the catalyst, the conversion rate of sec-octanone is only 70%, and the conversion rate is lower. Chinese patent application CN94190945A discloses a method for preparing a copper-containing hydrogenation catalyst, which requires a molded parent of the copper-containing hydrogenation catalyst, but has low selectivity, and the product is difficult to separate and purify. chinese patent application CN1279127a discloses a composite catalyst consisting of copper oxide, zinc oxide, magnesium oxide and aluminum oxide, the hydrogenation temperature is 150-300 ℃, the hydrogenation time is 8-15 hours, the conversion rate of sec-octyl ketone can reach 99.6%, but the catalyst preparation process is complex, and the hydrogenation time is long. Chinese patent application CN108774106A discloses an active carbon supported composite catalyst system, under the hydrogen flow of 3.5MPa and 120ml/min, the conversion rate of the sec-octyl ketone can reach 99.7% in 6 hours, but the catalyst described in the process is complex in preparation and high in cost. The German Hoechst company describes a Cu-ZnO-Al 2O3 catalyst in a patent application DE4244273A1, the hydrogenation selectivity of the catalyst and the yield of products are improved by adding Mo, mn, V, zr and other components into the catalyst as auxiliary agents, the addition proportion accounts for about 4 percent of the mass of CuO in the catalyst, the series of catalysts are applied to the hydrogenation reaction of sec-octanone, the yield of sec-octanol can reach about 96.5 percent, and the catalyst shows very high activity selectivity, however, the catalyst is complex to prepare and has high cost. Zhao Huiji et al in "hydrogenation reduction process for the preparation of high purity sec-octanol" (China university of Petroleum report) describe a sec-octanone hydrogenation catalyst prepared by co-precipitation-kneading, and the hydrogenation reaction is carried out under the following suitable process conditions: the reaction temperature is 120 ℃, the hydrogen pressure is 2.0MPa, the space velocity is 0.25h -1, the activity of the catalyst is evaluated under the condition, the result shows that the conversion rate of the sec-octyl ketone can reach about 98 percent, the purity of the sec-octyl alcohol in the hydrogenation product can reach about 98 percent, however, the catalyst preparation process is complex and takes a long time. Mebane RC et al in the journal of Synth Commun, described Raney nickel as a catalyst and isopropanol containing trace amounts of hydrochloric acid as a solvent, and could achieve conversion of ketone to secondary alcohol at reflux for 16-91 min with yields of 60-96%, but had the disadvantage of using hydrochloric acid and organic solvents, requiring removal of the organic solvents in the purification stage.
Disclosure of Invention
Problems to be solved by the invention
In view of the above-described drawbacks of the prior art, an object of the present invention is to provide a process for producing octanol which can obtain octanol with a high conversion in a short period of time, is simple in process, is mild in reaction conditions, and is particularly suitable for industrial mass production with high efficiency. In addition, the preparation method is also suitable for a crude sec-octanol system, can solve the problem of difficult separation of sec-octanol and sec-octanone, and simplifies the process for extracting refined sec-octanol by rectifying the crude sec-octanol.
Solution for solving the problem
The present inventors have made intensive studies to achieve the above object, and as a result, have found that the above object can be achieved by the implementation of the following means.
Namely, the present invention is as follows.
[1] A process for producing sec-octanol, wherein the process comprises the steps of:
a step of subjecting the secondary octanone to hydrogenation in the presence of a hydrogenation catalyst and a catalyst auxiliary agent,
Wherein the catalyst promoter comprises an acyclic carboxylic acid anhydride and/or a cyclic carboxylic acid anhydride.
[2] The production method according to [1], wherein the hydrogenation catalyst comprises at least one of a nickel-based catalyst, a copper-based catalyst and a noble metal-based catalyst.
[3] The production process according to [1] or [2], wherein the hydrogenation catalyst comprises a Raney nickel catalyst.
[4] The production method according to [1] or [2], wherein the catalyst auxiliary agent comprises phthalic anhydride.
[5] The production method according to any one of [1] to [4], wherein the hydrogenation reaction is carried out in an anhydrous system.
[6] The production method according to any one of [1] to [5], wherein the hydrogenation reaction satisfies one or more of the following conditions:
(i) The content of the hydrogenation catalyst is 0.34 to 38 mass%, preferably 0.5 to 38 mass%, more preferably 1 to 37.5 mass%, relative to the total amount of Zhong Xin ketone;
(ii) The content of the catalyst auxiliary is 0.08 to 10% by mass, preferably 0.1 to 10% by mass, more preferably 0.3 to 9.7% by mass, relative to the total amount of Zhong Xin ketone.
[7] The production process according to any one of [1] to [6], wherein the molar ratio of the secondary octanone to hydrogen is 1:0.8 to 1:1.1.
[8] The production method according to any one of [1] to [7], wherein the hydrogenation reaction satisfies one or more of the following conditions:
(I) The hydrogenation reaction temperature is 80-180 ℃, preferably 100-170 ℃;
(II) hydrogenation reaction pressure is 0.1-5 MPa, preferably 0.3-4.5 MPa;
The hydrogenation reaction time (III) is 0.3 to 10 hours, preferably 0.5 to 10 hours, more preferably 2 to 8 hours.
[9] The production process according to any one of [1] to [8], wherein the conversion of the secondary octanone is 99.9% or more.
[10] A secondary octanol, wherein the secondary octanol is obtained by the production method according to any one of [1] to [9 ].
ADVANTAGEOUS EFFECTS OF INVENTION
Compared with the prior art, the invention has the following technical effects:
(1) By using a hydrogenation catalyst in combination with a catalyst auxiliary, it has been unexpectedly found that the synergistic effect of the hydrogenation catalyst and the catalyst auxiliary can significantly improve the conversion rate of sec-octanone and shorten the reaction time, thereby achieving the production of sec-octanol at a high conversion rate in a short period of time.
(2) The manufacturing method of the invention has simple process and convenient operation.
(3) The manufacturing method of the invention has low investment cost and saves production cost.
(4) The preparation method has mild reaction conditions, low hydrogenation pressure and high conversion rate of the secondary octanone up to 99.9%.
(5) The preparation method of the invention is applicable to a crude sec-octanol system, namely, crude sec-octanol is taken as a raw material, the Zhong Xin ketone content in the crude sec-octanol is 7-15%, and the Zhong Xin ketone content after hydrogenation is reduced to below 0.03%, so that the problem of difficult separation of sec-octanol and sec-octanone can be solved, and the process for extracting refined sec-octanol by rectifying crude sec-octanol is simplified.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, the use of "optional" or "optional" means that certain substances, components, steps of performing, conditions of applying, etc. may or may not be used.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
In the present specification, unless specifically stated otherwise, "plural(s)" means that there are two or more.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
< Method for producing sec-octanol >
The method for producing the sec-octanol comprises the following steps:
a step of subjecting the secondary octanone to hydrogenation in the presence of a hydrogenation catalyst and a catalyst auxiliary agent,
Wherein the catalyst promoter comprises an acyclic carboxylic acid anhydride and/or a cyclic carboxylic acid anhydride.
In the invention, by combining the hydrogenation catalyst and the catalyst auxiliary agent in the hydrogenation reaction, the synergistic effect of the hydrogenation catalyst and the catalyst auxiliary agent is unexpectedly found, and the catalytic activity and selectivity are obviously improved, so that the conversion rate of the sec-octanone can be obviously improved, the reaction time is shortened, and the sec-octanol can be obtained with high conversion rate in a short time.
In addition, the manufacturing method of the invention has simple process, convenient operation and mild reaction conditions, and is particularly suitable for industrial large-scale and high-efficiency production. The preparation method is also suitable for a crude sec-octanol system, can solve the problem of difficult separation of sec-octanol and sec-octanone, and simplifies the process for extracting refined sec-octanol by rectifying crude sec-octanol.
(Sec-octanone)
In the present invention, commercially available secondary octanone may be used, and secondary octanone derived from a crude secondary octanol system may also be used.
As the crude sec-octanol system, a byproduct obtained by hydrolyzing castor oil to prepare sebacic acid or a crude sec-octanol mixed system containing unsaturated substances such as sec-octanone can be used. In the crude sec-octanol system, the Zhong Xin ketone content is, for example, 7 to 96% by mass.
(Hydrogenation catalyst)
In the production method of the present invention, the quality and yield of the product, i.e., the octanol, will be affected by the effect of the hydrogenation reaction. One of the factors for improving the effect of hydrogenation is to select a proper hydrogenation catalyst to increase the activity and selectivity of hydrogenation and reduce the generation of byproducts.
In the present invention, the hydrogenation catalyst comprises at least one of a nickel-based catalyst, a copper-based catalyst and a noble metal-based catalyst.
In some preferred embodiments, the nickel-based catalyst is preferably selected from either or a mixture of both supported nickel catalysts or Raney nickel catalysts.
The supported nickel catalyst is a catalyst in which active metallic nickel is supported on a carrier skeleton. From the viewpoint of high reactivity, a catalyst containing a compound in which nickel as a metal is supported on an inorganic compound as a carrier as a main component is preferable. Specific examples of the inorganic compound to be supported on the carrier include: silica, alumina, boria, silica-alumina, diatomaceous earth, clay, magnesia-silica (silica-magnesia), titania, zirconia, and the like.
In some preferred embodiments, the nickel-based catalyst is a raney nickel catalyst. As the Raney nickel catalyst, commercially available Raney nickel catalysts can be used, and examples thereof include: raney nickel catalyst (RC-2 Raney nickel catalyst) manufactured by Hongpeng catalyst Co., ltd.
The copper-based catalyst may be an unsupported catalyst or a supported catalyst. The unsupported catalyst is a mixture composed of an active component copper (Cu) and one or two or more of a transition metal oxide selected from cerium oxide, lanthanum oxide, samarium oxide, praseodymium oxide and yttrium oxide and/or a rare earth oxide selected from one or two or more of a transition metal oxide selected from cerium oxide, lanthanum oxide, samarium oxide, praseodymium oxide and yttrium oxide, preferably one or two of cerium oxide and lanthanum oxide, and one or more of a molybdenum oxide, preferably one or two of zinc oxide and iron oxide. The supported catalyst is composed of an active component copper (Cu) and a carrier, wherein the carrier is selected from one of alumina, silica, active carbon and zeolite, and the content of the active component copper (Cu) in the supported catalyst is 0.01-50wt%, preferably 1-20wt%, based on the total weight of the catalyst.
Examples of the noble metal-based catalyst include catalysts containing noble metals such as platinum, palladium, ruthenium, and rhodium as active components.
The shape of the hydrogenation catalyst is not particularly limited, and may be, for example, powder, granule, bar, or block.
< Catalyst auxiliary >
In the present invention, the catalyst auxiliary comprises an acyclic carboxylic acid anhydride and/or a cyclic carboxylic acid anhydride.
In some preferred embodiments, the acyclic carboxylic anhydride can include: chain carboxylic anhydrides such as acetic anhydride, propionic anhydride, succinic anhydride, and the like; aromatic carboxylic anhydrides such as benzoic anhydride.
Examples of the cyclic carboxylic acid anhydride include: maleic anhydride, phthalic anhydride, fumaric acid stem, succinic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.
In some preferred embodiments, the catalytic promoter is preferably phthalic anhydride. As phthalic anhydride, commercially available phthalic anhydride can be used, and examples thereof include: phthalic anhydride manufactured by microphone reagent company.
The shape of the catalyst auxiliary is not particularly limited, and may be, for example, powder, granule, bar, or block.
< Hydrogenation reaction >
In the hydrogenation reaction of the present invention, it is preferable to carry out the hydrogenation reaction by bringing the above-mentioned secondary octanone into contact with hydrogen in the presence of a hydrogenation catalyst and a catalyst auxiliary agent using a reactor such as a high-pressure reactor, thereby obtaining secondary octanol.
According to the present invention, the hydrogenation of the secondary octanone is carried out in a state substantially free of a solvent (e.g., water), i.e., in an anhydrous system. The invention can obtain the sec-octyl alcohol with high conversion rate in a short time by combining the hydrogenation catalyst and the catalyst auxiliary agent in an anhydrous system, and the obtained sec-octyl alcohol has the advantages of less impurities and the like.
In some preferred embodiments, the content of the hydrogenation catalyst is 0.34 to 38% by mass, preferably 0.5 to 38% by mass, more preferably 1 to 37.5% by mass, relative to the total amount of Zhong Xin ketone as a raw material. In some specific embodiments, the hydrogenation catalyst is present in an amount of 0.34, 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, or 38 mass%, relative to the total amount of Zhong Xin ketones as starting materials,
In some preferred embodiments, the content of the catalyst auxiliary is 0.08 to 10 mass%, preferably 0.1 to 10 mass%, more preferably 0.3 to 9.7 mass% with respect to the total amount of Zhong Xin ketone as a raw material. In some specific embodiments, the content of the catalytic promoter is 0.08 mass%, 0.5 mass%, 1 mass%, 1.5 mass%, 2 mass%, 2.5 mass%, 3 mass%, 3.5 mass%, 4 mass%, 4.5 mass%, 5 mass%, 5.5 mass%, 6 mass%, 6.5 mass%, 7 mass%, 7.5 mass%, 8 mass%, 8.5 mass%, 9 mass%, 9.5 mass%, or 10 mass% relative to the total amount of Zhong Xin ketones as starting materials.
In the present invention, when the hydrogenation catalyst and the catalytic auxiliary are used in combination in the above-mentioned content ranges, the synergistic effect can be more sufficiently exerted, the catalytic activity can be more advantageously improved, and thus the conversion rate of sec-octanone can be more remarkably improved, and the production of sec-octanol at a high conversion rate in a short time can be realized.
In some preferred embodiments, the molar ratio of the starting materials sec-octanone to hydrogen is preferably from 1:0.8 to 1:1.1, more preferably from 1:0.82 to 1:1.0.
In some preferred embodiments, the hydrogenation reaction temperature is preferably from 80 to 180 ℃, more preferably from 100 to 170 ℃. In some specific embodiments, the hydrogenation reaction temperature is 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, or 180 ℃. When the hydrogenation temperature is within the above range, the hydrogenation reaction can be sufficiently conducted, and sec-octanol can be obtained at a high conversion in a short time. If the hydrogenation reaction temperature is too low, the hydrogenation reaction is easily affected, so that the reaction time is too long or the reaction is not sufficiently carried out; on the other hand, if the hydrogenation reaction temperature is too high, side reactions may occur.
In some preferred embodiments, the hydrogenation reaction pressure is preferably from 0.1 to 5MPa, more preferably from 0.3 to 4.5MPa. In some specific embodiments, the hydrogenation reaction pressure is 0.5MPa, 1MPa, 2MPa, 3MPa, 4MPa, or 5MPa. When the hydrogenation pressure is within the above range, the hydrogenation reaction can be sufficiently conducted, and sec-octanol can be obtained at a high conversion in a short time.
In some preferred embodiments, the hydrogenation reaction time is preferably from 0.3 to 10 hours, more preferably from 0.5 to 10 hours, even more preferably from 2 to 8 hours. In some specific embodiments, the hydrogenation reaction time is 0.3h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, or 10h. When the hydrogenation time is within the above range, the hydrogenation reaction can be sufficiently conducted, and sec-octanol can be obtained at a high conversion in a short time.
The reaction form of the hydrogenation reaction is not particularly limited and may be carried out according to actual production requirements using a form of a reactor conventional in the art. From the viewpoint of reaction efficiency, an apparatus such as a high-pressure reactor is preferably used.
According to the production method of the present invention, the conversion rate of the secondary octanone can be significantly improved, and the conversion rate of the secondary octanone can be more than 99.5%, more preferably more than 99.9%. The production method of the present invention can obtain sec-octanol with a high conversion rate in a short time, relative to other production methods of sec-octanol.
In the production method of the present invention, after the hydrogenation reaction is completed, a separation step and/or a purification step may be further included. For example, after the hydrogenation reaction is completed, the separation and/or purification treatment is performed by a usual separation and purification operation such as filtration, extraction, distillation, or the like. The separation, purification and recovery of the sec-octanol are performed by a separation process and/or a purification process.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The materials used, or the instruments, unless otherwise specified, are conventional products available commercially.
The gas phase detection method of the content of the sec-octanol and Zhong Xin ketone comprises the following steps: the content of sec-octanone and sec-octanol was detected using Gas Chromatography (GC).
Specifically, agilent 7890A type gas chromatograph and HP-5 detection column use high purity nitrogen as carrier gas, the sample is prepared into solution with concentration of about 0.1g/ml by ethanol, the sample injection temperature is 80 ℃, the temperature is kept for 2min, the temperature is raised at 20 ℃/min rate until the end point temperature is 200 ℃, the detection temperature is 140 ℃, the sec-octanone retention time is 4.999min, the sec-octanol retention time is 5.058min, and the contents of the two are calculated by adopting an area normalization method.
The raw material sources are as follows: acetic anhydride, succinic anhydride, maleic anhydride, phthalic acid, acetic acid, succinic acid, and maleic acid in each example and comparative example are all pharmaceutical agents.
Example 1
Secondary octanone raw material 1: wherein Zhong Xin ketone content is 88.5%, feng Yi polymer material (manufactured by Lianyuangang Co., ltd.)
130G of the secondary octanone raw material 1 and 3.9g of Raney nickel catalyst (RC-2 Raney nickel catalyst, ind. Kyowa Co., ltd.) are added into a 250mL high-pressure reaction kettle with mechanical stirring, then 1.0g of catalyst auxiliary agent phthalic anhydride is added, after three times of replacement by nitrogen, hydrogen is used for replacing twice, then hydrogen is filled to the pressure of 1.0MPa, the high-pressure reaction kettle is heated to 100 ℃ under the stirring condition, the hydrogen pressure is regulated to 2.7MPa, after the reaction starts, the hydrogen pressure of the system is gradually reduced, the hydrogen pressure is regulated, the hydrogen pressure is maintained to 2.7MPa, the reaction is continued, the secondary octanone content in the system is periodically sampled and detected in the reaction process, the reaction is ended, cooling is carried out, the surplus pressure is released, the material is taken out, and the Zhong Xin ketone content is detected by Gas Chromatography (GC). The detection result shows that the Zhong Xin ketone content is 0.09% after 2 hours, the conversion rate is 99.9%, and the sec-octanol content is 98.6%.
Conversion = (content of secondary octanone before hydrogenation-content of secondary octanone after hydrogenation)/content of Zhong Xin ketone before hydrogenation × 100%
Example 2
Secondary octanone raw material 2: wherein Zhong Xin ketone content is 8%, feng Yi polymer material (manufactured by Lianyong Co., ltd.)
Octanol was produced in the same manner as in example 1, except that the above-mentioned octanone starting material 2 was used as a starting material instead of the octanone starting material 1. GC detection results show that the Zhong Xin ketone content is 0.02% after 2 hours, the conversion is 99.8%, and the sec-octanol content is 98.3%.
Example 3
Sec-octanol was produced in the same manner as in example 1, except that the amount of Raney nickel catalyst was changed to 1.15 g. GC detection results show that the Zhong Xin ketone content is 0.11% after 6 hours, the conversion is 99.8%, and the sec-octanol content is 98.6%.
Example 4
Sec-octanol was produced in the same manner as in example 1, except that the amount of the catalyst auxiliary phthalic anhydride was changed to 1.5 g. GC detection results show that the Zhong Xin ketone content is 0.07% after 2 hours, the conversion is 99.9%, and the sec-octanol content is 98.7%.
Example 5
Sec-octanol was produced in the same manner as in example 1, except that the amount of the catalyst auxiliary phthalic anhydride was changed to 0.5 g. GC detection results show that the Zhong Xin ketone content is 0.12% after 7h, the conversion is 99.8%, and the sec-octanol content is 98.5%.
Example 6
Sec-octanol was produced in the same manner as in example 1, except that the hydrogenation temperature was lowered to 80 ℃. GC detection results show that the Zhong Xin ketone content is 7.1% after 10 hours, the conversion is 92.1%, and the sec-octanol content is 91.4%.
Example 7
Sec-octanol was produced in the same manner as in example 1, except that the hydrogenation temperature was increased to 120 ℃. GC detection results show that the Zhong Xin ketone content is 0.10% after 2 hours, the conversion is 99.9%, and the sec-octanol content is 98.5%.
Example 8
Sec-octanol was produced in the same manner as in example 1, except that the hydrogenation pressure was lowered to 0.5 MPa. GC detection results show that the Zhong Xin ketone content is 0.29% after 10 hours, the conversion is 99.7%, and the sec-octanol content is 98.1%.
Example 9
Sec-octanol was produced in the same manner as in example 1, except that the hydrogenation pressure was increased to 3.0 MPa. GC detection results show that the Zhong Xin ketone content is 0.12% after 2 hours, the conversion is 99.8%, and the sec-octanol content is 98.3%.
Example 10
Sec-octanol was produced in the same manner as in example 1, except that the hydrogenation time was changed to 1 h. GC detection results show that the Zhong Xin ketone content is 3.6% after 1h, the conversion is 96.0%, and the sec-octanol content is 95.2%.
Example 11
Sec-octanol was produced in the same manner as in example 1, except that 1.0g of acetic anhydride was used as a catalyst auxiliary instead of phthalic anhydride. GC detection results show that the Zhong Xin ketone content is 0.14% after 2 hours, the conversion is 99.8%, and the sec-octanol content is 98.6%.
Example 12
Sec-octanol was produced in the same manner as in example 1, except that 1.0g of succinic anhydride was used as a catalyst auxiliary instead of phthalic anhydride. GC detection results show that the Zhong Xin ketone content is 0.12% after 2 hours, the conversion is 99.8%, and the sec-octanol content is 98.7%.
Example 13
Sec-octanol was produced in the same manner as in example 1, except that 1.0g of maleic anhydride was used as a catalyst auxiliary instead of phthalic anhydride. GC detection results show that the Zhong Xin ketone content is 0.11% after 2 hours, the conversion is 99.8%, and the sec-octanol content is 98.6%.
Example 14
Sec-octanol was produced in the same manner as in example 1, except that the amount of the catalyst auxiliary phthalic anhydride was reduced to 0.1 g. GC detection results show that the Zhong Xin ketone content is 34.5% after 10 hours, the conversion is 61.1% and the sec-octanol content is 64.3%.
Example 15
Sec-octanol was produced in the same manner as in example 1, except that the amount of Raney nickel hydrogenation catalyst was reduced to 0.4 g. GC detection results show that the Zhong Xin ketone content is 21.3% after 10 hours, the conversion is 76.0%, and the sec-octanol content is 77.3%.
Example 16
Sec-octanol was produced in the same manner as in example 1, except that the hydrogenation time was changed to 0.3 h. GC detection results show that the Zhong Xin ketone content is 23.7% after 0.3h, the conversion is 73.3% and the sec-octanol content is 75.1%.
Comparative example 1
Secondary octanone raw material 1: wherein Zhong Xin ketone content is 88.5%, feng Yi polymer material (manufactured by Lianyuangang Co., ltd.)
130G of secondary octanone raw material 1 and 3.9g of Raney nickel catalyst (RC-2 Raney nickel catalyst, ind. Kyowa catalyst Co., ltd., REW.) are added into a 250mL high-pressure reaction kettle with mechanical stirring, after three times of replacement by nitrogen, hydrogen is used for replacing twice, then hydrogen is filled to the pressure of 1.0MPa, the high-pressure reaction kettle is heated to 100 ℃ under the stirring condition, the hydrogen pressure is regulated to 2.7MPa, after the reaction starts, the hydrogen pressure of the system is gradually reduced, the hydrogen pressure is regulated, the hydrogen pressure is maintained to 2.7MPa, the reaction is continued, the secondary octanone content in the system is periodically sampled and detected in the reaction process, the reaction is ended, the excess pressure is released, the materials are taken out, and the content of Zhong Xin ketone is detected by GC. The detection result shows that the Zhong Xin ketone content is 80.0% after 6 hours, the conversion rate is 9.6%, and the sec-octanol content is 19.5%.
Comparative example 2
Sec-octanol was produced in the same manner as in comparative example 1, except that 1.0g of a catalyst auxiliary phthalic acid was added. GC detection results show that the Zhong Xin ketone content is 81.2% after 6 hours, the conversion is 8.2% and the sec-octanol content is 18.3%.
Comparative example 3
Octanol was produced in the same manner as in comparative example 1, except that the above-mentioned octanone raw material 2 was used as a raw material. GC detection results show that the Zhong Xin ketone content is 7.1% after 6 hours, the conversion is 11.2%, and the sec-octanol content is 91.4%.
Comparative example 4
Sec-octanol was produced in the same manner as in comparative example 3, except that 1.0g of a catalyst auxiliary phthalic acid was added. GC detection results show that the Zhong Xin ketone content is 7.3% after 6 hours, the conversion is 8.75%, and the sec-octanol content is 90.9%.
Comparative example 5
Sec-octanol was produced in the same manner as in comparative example 1, except that 1.0g of acetic acid was added as a catalyst auxiliary. GC detection results show that the Zhong Xin ketone content is 81.8% after 5 hours, the conversion is 7.57% and the sec-octanol content is 16.7%.
Comparative example 6
Sec-octanol was produced in the same manner as in comparative example 1, except that 1.0g of succinic acid was added as a catalyst auxiliary. GC detection results show that the Zhong Xin ketone content is 79.3% after 5 hours, the conversion is 10.4%, and the sec-octanol content is 20.5%.
Comparative example 7
Octanol was produced in the same manner as in comparative example 1, except that 1.0g of maleic acid was added as a catalyst auxiliary. GC detection results show that the Zhong Xin ketone content is 80.1% after 5 hours, the conversion is 9.5%, and the sec-octanol content is 18.3%.
Industrial applicability
The preparation method of the invention can obtain the sec-octyl alcohol with high conversion rate in a short time, has simple process, convenient operation and mild reaction condition, and is particularly suitable for industrial large-scale and high-efficiency production. In addition, the preparation method is also suitable for a crude sec-octanol system, can solve the problem of difficult separation of sec-octanol and sec-octanone, and simplifies the process for extracting refined sec-octanol by rectifying the crude sec-octanol.
Claims (10)
1. A method for producing sec-octanol, comprising the steps of:
a step of subjecting the secondary octanone to hydrogenation in the presence of a hydrogenation catalyst and a catalyst auxiliary agent,
Wherein the catalyst auxiliary agent is acyclic carboxylic anhydride and/or cyclic carboxylic anhydride,
The hydrogenation catalyst is Raney nickel catalyst,
The hydrogenation reaction is carried out in an anhydrous system.
2. The method according to claim 1, wherein the catalyst auxiliary is phthalic anhydride, acetic anhydride, succinic anhydride or maleic anhydride.
3. The manufacturing method according to claim 1 or 2, characterized in that the hydrogenation reaction satisfies one or more of the following conditions:
(i) The content of the hydrogenation catalyst is 0.34-38% by mass relative to the total amount of Zhong Xin ketone;
(ii) The content of the catalyst auxiliary is 0.08 to 10 mass% relative to the total amount of Zhong Xin ketone.
4. The manufacturing method according to claim 1 or 2, characterized in that the hydrogenation reaction satisfies one or more of the following conditions:
(i) The content of the hydrogenation catalyst is 0.5-38% by mass relative to the total amount of Zhong Xin ketone;
(ii) The content of the catalyst auxiliary is 0.1 to 10 mass% relative to the total amount of Zhong Xin ketone.
5. The manufacturing method according to claim 1 or 2, characterized in that the hydrogenation reaction satisfies one or more of the following conditions:
(i) The content of the hydrogenation catalyst is 1 to 37.5 mass% relative to the total amount of Zhong Xin ketone;
(ii) The content of the catalyst auxiliary is 0.3 to 9.7 mass% relative to the total amount of Zhong Xin ketone.
6. The production method according to claim 1 or 2, wherein the molar ratio of the secondary octanone to the hydrogen gas is 1:0.8 to 1:1.1.
7. The manufacturing method according to claim 1 or 2, characterized in that the hydrogenation reaction satisfies one or more of the following conditions:
(I) The hydrogenation reaction temperature is 80-180 ℃;
(II) hydrogenation reaction pressure is 0.1-5 MPa;
the hydrogenation reaction time of (III) is 0.3-10 h.
8. The manufacturing method according to claim 1 or 2, characterized in that the hydrogenation reaction satisfies one or more of the following conditions:
(I) The hydrogenation reaction temperature is 100-170 ℃;
(II) hydrogenation reaction pressure is 0.3-4.5 MPa;
The hydrogenation reaction time of (III) is 0.5-10 h.
9. The process according to claim 7, wherein the hydrogenation reaction time is 2 to 8 hours.
10. The production method according to claim 1 or 2, wherein the conversion rate of the secondary octanone is 99.9% or more.
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| CN1346703A (en) * | 2001-09-11 | 2002-05-01 | 中国石油天然气股份有限公司 | Method for preparing sec-octanol by sec-octanone hydrogenation and nickel-containing catalyst thereof |
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| CN1346703A (en) * | 2001-09-11 | 2002-05-01 | 中国石油天然气股份有限公司 | Method for preparing sec-octanol by sec-octanone hydrogenation and nickel-containing catalyst thereof |
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