CN115974649A

CN115974649A - Method for preparing sec-octanol

Info

Publication number: CN115974649A
Application number: CN202211699796.5A
Authority: CN
Inventors: 崔兵; 杜青慧; 苏永胜
Original assignee: Wilmar Highpolymer Material Lianyungang Co Ltd
Current assignee: Wilmar Highpolymer Material Lianyungang Co Ltd
Priority date: 2022-12-28
Filing date: 2022-12-28
Publication date: 2023-04-18

Abstract

The invention provides a method for producing sec-octanol. The method for producing sec-octanol of the present invention comprises the steps of: a step of hydrogenating Zhong Xintong in the presence of a hydrogenation catalyst and a promoter, wherein the promoter comprises an acyclic carboxylic acid anhydride and/or a cyclic carboxylic acid anhydride. The preparation method can obtain the sec-octanol at high conversion rate in a short time, has simple process, convenient operation and mild reaction conditions, 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 that the separation of sec-octanol and Zhong Xintong is difficult, and simplifies the process for extracting refined sec-octanol by rectifying crude sec-octanol.

Description

Method for preparing sec-octanol

Technical Field

The invention belongs to the field of fine chemical engineering, and relates to a method for preparing sec-octanol.

Background

Aliphatic alcohol and aliphatic ketone are important chemical raw materials, and in industrial production, hydrogenation of ketone to prepare alcohol is the most common method.

The secondary octanol is an important chemical raw material and an organic solvent, and can be used as a wetting agent, a spice, a plasticizer and a pesticide emulsifier, and also can be used as a raw material for producing high-grade lubricating oil additives. The secondary octanol is mainly derived from a byproduct of preparing sebacic acid by hydrolyzing castor oil, generally, the content of 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 octanol is limited. There are generally two methods for preparing high-purity sec-octanol by using industrial sec-octanol as a raw material: one is chemical method with NaHSO ₃ Washing the solution, and separating 2-octanone to obtain secondary octanol and 2-octanone; another method is a hydrogenation method; hydrogenating the 2-octanone in the sec-octanol to reduce it into sec-octanol. The expected result cannot be achieved by chemical treatment, 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 patent literature report of Zhong Xintong preparing sec-octanol by hydrogenation currently, chinese patent application CN1974514a discloses a research on preparation of sec-octanol by hydrogenation of Zhong Xintong on a magnetic reaction fixed bed with a ferromagnetic catalyst, 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 Zhong Xintong is only 70%, and the conversion rate is low. Chinese patent application CN94190945a discloses a preparation method of a copper-containing hydrogenation catalyst, which requires a formed precursor of the copper-containing hydrogenation catalyst, but has low selectivity and difficult product separation and purification. Chinese patent application CN1279127A discloses a composite catalyst composed 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 Zhong Xintong can reach 99.6%, but the catalyst preparation process is complex, and the hydrogenation time is long. Chinese patent application CN108774106A discloses an activated carbon-supported composite catalyst system, under the hydrogen flow of 120ml/min under 3.5MPa, the conversion rate of sec-octanone can reach 99.7% within 6h, but the catalyst described in the process is complex to prepare and has high cost. Germany Hoechst company introduces a Cu-ZnO-Al in patent application DE4244273A1 ₂ O ₃ The catalyst is added with Mo, mn, V, zr and other components as assistant to raise the hydrogenation selectivity and product yield, and the added proportion accounts for about 4% of CuO mass in the catalyst, and when the series of catalysts are applied in the hydrogenation reaction of Zhong Xintong, the yield of sec-octanol can reach about 96.5%, and high activity selectivity is shown, but the catalyst is complex to prepare and has high cost. Zhao Huiji, et al, in the preparation of high-purity sec-octanol by hydrogenation reduction (reported in university of petroleum, china) describe a sec-octanone hydrogenation catalyst, which is prepared by coprecipitation-kneading, and the hydrogenation reaction is carried out under the appropriate process conditions: the reaction temperature is 120 ℃, the hydrogen pressure is 2.0MPa, and the space velocity is 0.25h ^-1 The activity of the catalyst is evaluated under the condition, and the result shows that the conversion rate of Zhong Xintong can reach about 98 percent, and the purity of the sec-octanol in the hydrogenation product can reach about 98 percent, but the preparation process of the catalyst is complex and consumes long time. Mebane RC et al, 2007 in the Synth Commun journal, introduced Raney nickel as a catalyst and isopropanol containing a trace amount of hydrochloric acid as a solvent, could achieve conversion of ketones to secondary alcohols at 60-96% yield under reflux conditions for 16-91 min, but had the disadvantage of using hydrochloric acid and an organic solvent, requiring removal of the organic solvent in the purification stage.

Disclosure of Invention

Problems to be solved by the invention

In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for producing sec-octanol, which can produce sec-octanol at a high conversion rate in a short time, and which is simple in process, mild in reaction conditions, and 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 Zhong Xintong, and simplifies the process for extracting refined sec-octanol by rectifying crude sec-octanol.

Means for solving the problems

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 carrying out the following means.

Namely, the present invention is as follows.

[1] A method for producing sec-octanol, wherein the method comprises the steps of:

a step of subjecting Zhong Xintong to a hydrogenation reaction in the presence of a hydrogenation catalyst and a catalyst promoter,

wherein the catalyst promoter comprises acyclic carboxylic acid anhydride and/or cyclic carboxylic acid anhydride.

[2] The production process 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 co-catalyst comprises phthalic anhydride.

[5] The production process 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% by mass, preferably 0.5 to 38% by mass, and more preferably 1 to 37.5% by mass, based on the total amount of Zhong Xintong;

(ii) The content of the promoter is 0.08 to 10% by mass, preferably 0.1 to 10% by mass, and more preferably 0.3 to 9.7% by mass, based on the total amount of Zhong Xintong.

[7] The production method according to any one of [1] to [6], wherein a molar ratio of Zhong Xintong to hydrogen gas is 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 ℃, and preferably 100-170 ℃;

(II) the hydrogenation 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, and more preferably 2 to 8 hours.

[9] The production method according to any one of [1] to [8], wherein the conversion rate of Zhong Xintong is 99.9% or more.

[10] A sec-octanol 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) Through the combined use of the hydrogenation catalyst and the catalytic promoter, the synergistic effect of the hydrogenation catalyst and the catalytic promoter is unexpectedly found, the conversion rate of the sec-octanone can be remarkably improved, the reaction time is shortened, and the sec-octanol can be obtained at a high conversion rate in a short 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 and low hydrogenation pressure, and the conversion rate of Zhong Xintong can reach 99.9 percent.

(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 content of sec-octanone in the crude sec-octanol is 7-15%, and the content of sec-octanone after hydrogenation is reduced to be below 0.03%, so that the problem of difficult separation of sec-octanol and Zhong Xintong can be solved, and the process for extracting refined sec-octanol by rectifying crude sec-octanol is simplified.

Detailed Description

The present invention will be described in detail below. The technical features described below are explained based on typical 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 represented by "numerical value a to numerical value B" means a range including an end point numerical value A, B.

In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.

In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

As used herein, the term "optional" or "optional" is used to indicate that certain substances, components, performance steps, application conditions, and the like are used or not used.

In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.

In the present specification, the term "plurality" means two or more than two unless otherwise specified.

Reference in the specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "embodiments," 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 described elements may be combined in any suitable manner in the various embodiments.

< Process for producing Secondary octanol >

The method for producing sec-octanol of the present invention comprises the steps of:

In the invention, the hydrogenation catalyst and the catalytic promoter are used in the hydrogenation reaction in a combined manner, and the synergistic effect of the hydrogenation catalyst and the catalytic promoter is unexpectedly found, so that the catalytic activity and the selectivity are remarkably improved, the conversion rate of sec-octanone can be remarkably improved, the reaction time is shortened, and the sec-octanol can be obtained at high conversion rate in a short time.

In addition, the preparation method 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 that the separation of sec-octanol and Zhong Xintong is difficult, and simplifies the process for extracting refined sec-octanol by rectifying crude sec-octanol.

(Zhong Xintong)

In the present invention, zhong Xintong, which is commercially available, or Zhong Xintong, which is derived from a crude sec-octanol system, can be used as the sec-octanone.

The crude sec-octanol system may be a by-product obtained by hydrolyzing castor oil to prepare sebacic acid, or a crude sec-octanol mixed system containing an unsaturated substance such as Zhong Xintong. In the crude sec-octanol system, the sec-octanone content is, for example, 7 to 96% by mass.

(hydrogenation catalyst)

In the production process of the present invention, the quality of the hydrogenation reaction affects the quality and yield of the sec-octanol product. One of the factors for improving the hydrogenation effect is to select a suitable hydrogenation catalyst to increase the hydrogenation activity and selectivity and reduce the formation of by-products.

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 supported nickel catalysts or raney nickel catalysts.

The supported nickel catalyst is a catalyst in which an active metal nickel is supported on a support skeleton. From the viewpoint of high reactivity, a catalyst containing, as a main component, a compound in which nickel as a metal is supported on an inorganic compound as a carrier is preferable. Specific examples of the supported inorganic compound of 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: a raney nickel catalyst (RC-2 raney nickel catalyst) manufactured by jingjiang city macropec catalyst limited, and the like.

The copper-based catalyst may be an unsupported catalyst or a supported catalyst. The unsupported catalyst is a mixture of active components of copper (Cu) and transition metal oxide and/or rare earth oxide, wherein the transition metal oxide is selected from one or two or more of nickel oxide, zinc oxide, chromium oxide, iron oxide, cobalt oxide and molybdenum oxide, preferably one or two of zinc oxide and iron oxide, and the rare earth oxide is selected from one or two or more of cerium oxide, lanthanum oxide, samarium oxide, praseodymium oxide and yttrium oxide, preferably one or two of cerium oxide and lanthanum oxide. The supported catalyst consists of active component copper (Cu) and carrier, 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 0.01-50 wt%, preferably 1-20 wt%, based on the total weight of the catalyst.

Examples of the noble metal-based catalyst include catalysts containing a noble metal such as platinum, palladium, ruthenium, and rhodium as an active component.

The shape of the hydrogenation catalyst is not particularly limited, and may be, for example, a powder, a granule, a bar or a block.

< catalyst auxiliary >

In the present invention, the co-catalyst comprises an acyclic carboxylic acid anhydride and/or a cyclic carboxylic acid anhydride.

In some preferred embodiments, the acyclic carboxylic acid anhydride may include: chain carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and succinic anhydride; such as aromatic carboxylic acid anhydrides like benzoic anhydride.

Examples of the cyclic carboxylic acid anhydride include: maleic anhydride, phthalic anhydride, fumaric acid, succinic anhydride, itaconic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.

In some preferred embodiments, the co-catalyst is preferably phthalic anhydride. As phthalic anhydride, commercially available phthalic anhydride can be used, and examples thereof include: phthalic anhydride manufactured by mclin reagents inc.

The shape of the catalyst promoter is not particularly limited, and may be, for example, a powder, a granule, a bar or a block.

< hydrogenation reaction >

In the hydrogenation reaction of the present invention, it is preferable to use a reactor such as an autoclave to contact the Zhong Xintong with hydrogen in the presence of both a hydrogenation catalyst and a catalyst promoter to perform a hydrogenation reaction, thereby obtaining sec-octanol.

According to the present invention, the hydrogenation reaction of Zhong Xintong is carried out in an anhydrous system which is substantially free of a solvent (e.g., water). According to the invention, the hydrogenation catalyst and the catalytic assistant are used in an anhydrous system in a combined manner, so that the sec-octanol can be obtained at a high conversion rate in a short time, and the obtained sec-octanol has the advantages of few 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, and more preferably 1 to 37.5% by mass, relative to the total amount of the secondary octanones as the raw material. In some specific embodiments, the content of the hydrogenation catalyst is 0.34 mass%, 1 mass%, 2 mass%, 3 mass%, 4 mass%, 5 mass%, 6 mass%, 7 mass%, 8 mass%, 9 mass%, 10 mass%, 15 mass%, 20 mass%, 25 mass%, 30 mass%, 35 mass%, or 38 mass% with respect to the total amount of the secondary octanones as the raw material,

In some preferred embodiments, the content of the catalyst aid is 0.08 to 10% by mass, preferably 0.1 to 10% by mass, and more preferably 0.3 to 9.7% by mass, relative to the total amount of the secondary octanones as the raw material. In some specific embodiments, the content of the catalyst aid 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% with respect to the total amount of the secondary octanones as the raw material.

In the present invention, when the hydrogenation catalyst and the catalyst promoter are used in combination at the same time in the above-mentioned content ranges, the synergistic effect can be more sufficiently exerted, and the catalytic activity can be more favorably improved, so that the conversion rate of sec-octanone can be more remarkably increased, 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 feedstock Zhong Xintong to hydrogen is preferably from 1.

In some preferred embodiments, the hydrogenation reaction temperature is preferably from 80 to 180 deg.C, more preferably from 100 to 170 deg.C. In some specific embodiments, the hydrogenation reaction temperature is 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ or 180 ℃. When the hydrogenation reaction temperature is within the above range, the hydrogenation reaction can be sufficiently performed, and sec-octanol can be obtained at a high conversion rate in a short time. If the hydrogenation reaction temperature is too low, the hydrogenation reaction is easily influenced, 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 performed, 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, and 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 reaction time is within the above range, the hydrogenation reaction can be sufficiently performed, and sec-octanol can be obtained at a high conversion rate in a short time.

The reaction form of the hydrogenation reaction is not particularly limited and may be carried out by using a form of a reactor which is conventional in the art according to actual production needs. From the viewpoint of reaction efficiency, an apparatus such as a high-pressure reactor is preferably used.

According to the preparation method, the conversion rate of the sec-octanone can be remarkably improved, and the conversion rate of Zhong Xintong can reach more than 99.5 percent, and more preferably more than 99.9 percent. The production method of the present invention can produce a sec-octanol at a high conversion rate in a short time, compared to other production methods of a sec-octanol.

The production method of the present invention may further comprise a separation step and/or a purification step after the completion of the hydrogenation reaction. For example, after the completion of the hydrogenation reaction, the reaction mixture is subjected to a separation and/or purification treatment 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 carried out 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 those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The materials or apparatuses used are, unless otherwise specified, conventional products commercially available may be used.

The gas phase detection method for the content of the secondary octanol and the secondary octanone comprises the following steps: the content of Zhong Xintong and sec-octanol was measured using Gas Chromatography (GC).

Specifically, an Agilent 7890A type gas chromatograph and an HP-5 detection column are characterized in that high-purity nitrogen is used as carrier gas, a sample is prepared into a solution with the concentration of about 0.1g/ml by using ethanol, the sample introduction temperature is 80 ℃, the temperature is increased at the speed of 20 ℃/min after being kept for 2min until the end point temperature is 200 ℃, the detection temperature is 140 ℃, the retention time of Zhong Xintong is 4.999min, the retention time of sec-octanol is 5.058min, and the contents of the two are measured 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 were all national reagents.

Example 1

Zhong Xintong feedstock 1: wherein the content of sec-octanone is 88.5%, feng Yi made by Polymer materials (Liyunggang) Co., ltd

130g of the Zhong Xintong raw material 1 and 3.9g of a raney nickel catalyst (RC-2 raney nickel catalyst, macropeng catalyst Co., jingjiang city) are added into a 250mL high-pressure reaction kettle with mechanical stirring, 1.0g of catalytic assistant phthalic anhydride is added, nitrogen is used for replacing for three times, then hydrogen is used for replacing for two times, then hydrogen is filled until the pressure is 1.0MPa, the high-pressure reaction kettle is heated to 100 ℃ under the stirring condition, the hydrogen pressure is adjusted to 2.7MPa, the hydrogen pressure of the system is gradually reduced after the reaction starts, the hydrogen pressure is adjusted to maintain the hydrogen pressure to be 2.7MPa, the reaction is continued, the content of the sec-octanone in the system is detected by sampling at regular time in the reaction process, the reaction is finished, the cooling is carried out, the pressure is released, the material is taken out, and the content of the sec-octanone is detected by a Gas Chromatography (GC). The detection result shows that after 2 hours, the content of the sec-octanone is 0.09%, the conversion rate is 99.9%, and the content of the sec-octanol is 98.6%.

Conversion = (sec-octanone content before hydrogenation-sec-octanone content after hydrogenation)/sec-octanone content before hydrogenation × 100%

Example 2

Zhong Xintong feedstock 2: wherein the content of sec-octanone is 8%, feng Yi made by Polymer materials (Liyunggang) Co., ltd

Sec-octanol was produced in the same manner as in example 1, except that the above-described sec-octanone starting material 2 was used as a starting material in place of the sec-octanone starting material 1. GC detection results show that after 2 hours, the content of the sec-octanone is 0.02 percent, the conversion rate is 99.8 percent, and the content of the sec-octanol is 98.3 percent.

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 after 6 hours, the content of the sec-octanone is 0.11%, the conversion rate is 99.8%, and the content of the sec-octanol is 98.6%.

Example 4

Sec-octanol was produced in the same manner as in example 1, except that the amount of the co-agent phthalic anhydride was changed to 1.5 g. GC detection results show that after 2h, the sec-octanone content is 0.07%, the conversion rate 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 co-agent phthalic anhydride was changed to 0.5 g. GC detection results show that after 7h, the sec-octanone content is 0.12%, the conversion rate 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 analysis showed that after 10h, the sec-octanone content was 7.1%, the conversion was 92.1% and the sec-octanol content was 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 after 2h, the sec-octanone content is 0.10%, the conversion rate 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 reduced to 0.5 MPa. GC detection results show that after 10h, the sec-octanone content is 0.29%, the conversion rate 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 after 2h, the sec-octanone content is 0.12%, the conversion rate 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 after 1h, the sec-octanone content is 3.6%, the conversion rate is 96.0%, and the sec-octanol content is 95.2%.

Example 11

Secondary octanol was produced in the same manner as in example 1, except that 1.0g of acetic anhydride was used as the co-catalyst in place of phthalic anhydride. GC detection results show that after 2h, the sec-octanone content is 0.14%, the conversion rate 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 instead of phthalic anhydride as the co-catalyst. GC detection results show that after 2h, the sec-octanone content is 0.12%, the conversion rate 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 co-catalyst instead of phthalic anhydride. GC detection results show that after 2h, the sec-octanone content is 0.11%, the conversion rate 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 promoter phthalic anhydride was reduced to 0.1 g. GC analysis showed that after 10h the sec-octanone content was 34.5%, the conversion was 61.1% and the sec-octanol content was 64.3%.

Example 15

Sec-octanol was produced in the same manner as in example 1, except that the amount of raney nickel used as a hydrogenation catalyst was reduced to 0.4 g. GC detection results show that after 10h, the sec-octanone content is 21.3%, the conversion is 76.0%, and the sec-octanol content is 77.3%.

Example 16

Secondary octanol was produced in the same manner as in example 1, except that the hydrogenation time was changed to 0.3 h. GC analysis showed that after 0.3h, the sec-octanone content was 23.7%, the conversion was 73.3% and the sec-octanol content was 75.1%.

Comparative example 1

Adding 130g of Zhong Xintong raw material 1 and 3.9g of Raney nickel catalyst (RC-2 Raney nickel catalyst, macropeng catalyst Co., jingjiang city) into a 250mL high-pressure reaction kettle with mechanical stirring, replacing the mixture with nitrogen for three times, replacing the mixture with hydrogen for two times, then filling hydrogen into the high-pressure reaction kettle until the pressure is 1.0MPa, heating the high-pressure reaction kettle to 100 ℃ under the stirring condition, adjusting the hydrogen pressure to 2.7MPa, gradually reducing the hydrogen pressure of the system after the reaction starts, adjusting the hydrogen pressure, maintaining the hydrogen pressure to 2.7MPa, continuing the reaction, sampling and detecting the content of sec-octanone in the system at regular time in the reaction process, cooling after the reaction finishes, releasing the excess pressure, taking out the material, and detecting the content of sec-octanone by GC. The detection result shows that after 6 hours, the content of the sec-octanone is 80.0 percent, the conversion rate is 9.6 percent, and the content of the sec-octanol is 19.5 percent.

Comparative example 2

Secondary octanol was produced in the same manner as in comparative example 1, except that 1.0g of the co-agent phthalic acid was added. GC detection results show that after 6h, the sec-octanone content is 81.2%, the conversion rate is 8.2%, and the sec-octanol content is 18.3%.

Comparative example 3

Secondary octanol was produced in the same manner as in comparative example 1, except that the above-described secondary octanone starting material 2 was used as the starting material. GC detection shows that after 6h, the sec-octanone content is 7.1%, the conversion is 11.2% and the sec-octanol content is 91.4%.

Comparative example 4

Secondary octanol was produced in the same manner as in comparative example 3, except that 1.0g of the catalytic assistant phthalic acid was added. GC detection results show that after 6h, the sec-octanone content is 7.3%, the conversion is 8.75%, and the sec-octanol content is 90.9%.

Comparative example 5

Secondary 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 shows that after 5h, the sec-octanone content is 81.8%, the conversion is 7.57% and the sec-octanol content is 16.7%.

Comparative example 6

Secondary octanol was produced in the same manner as in comparative example 1, except that 1.0g of succinic acid was added as a catalyst aid. GC detection shows that after 5h, the sec-octanone content is 79.3%, the conversion is 10.4% and the sec-octanol content is 20.5%.

Comparative example 7

Sec-octanol was produced in the same manner as in comparative example 1, except that 1.0g of maleic acid was added as a catalyst assistant. GC detection results show that after 5h, the sec-octanone content is 80.1%, the conversion is 9.5%, and the sec-octanol content is 18.3%.

Industrial applicability

The preparation method can obtain the sec-octanol at high conversion rate in a short time, has simple process, convenient operation and mild reaction conditions, and is particularly suitable for large-scale and high-efficiency industrial 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 Zhong Xintong, and simplifies the process for extracting refined sec-octanol by rectifying crude sec-octanol.

Claims

1. A method for producing sec-octanol, comprising the steps of:

a step of hydrogenating Zhong Xintong in the presence of a hydrogenation catalyst and a promoter, wherein the promoter comprises an acyclic carboxylic acid anhydride and/or a cyclic carboxylic acid anhydride.

2. The production method according to claim 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 method according to claim 1 or 2, characterized in that the hydrogenation catalyst comprises a raney nickel catalyst.

4. The production method according to claim 1 or 2, wherein the co-catalyst comprises phthalic anhydride.

5. The production method according to any one of claims 1 to 4, wherein the hydrogenation reaction is carried out in an anhydrous system.

6. The production method according to any one of claims 1 to 5, wherein the hydrogenation reaction satisfies one or more of the following conditions:

(ii) The content of the catalyst promoter is 0.08 to 10% by mass, preferably 0.1 to 10% by mass, and more preferably 0.3 to 9.7% by mass, based on the total amount of Zhong Xintong.

7. The method of manufacturing according to any one of claims 1-6, wherein the molar ratio of Zhong Xintong to hydrogen is 1.8-1.1.

8. The production method according to any one of claims 1 to 7, wherein the hydrogenation reaction satisfies one or more of the following conditions:

(II) the hydrogenation pressure is 0.1-5 MPa, preferably 0.3-4.5 MPa;

the hydrogenation reaction time of (III) is 0.3 to 10 hours, preferably 0.5 to 10 hours, and more preferably 2 to 8 hours.

9. The method of any one of claims 1-8, wherein the conversion of Zhong Xintong is 99.9% or greater.

10. A sec-octanol obtained by the production method according to any one of claims 1 to 9.