CN107089899B - Method for preparing n-octanol by adopting supported bimetallic catalyst - Google Patents

Method for preparing n-octanol by adopting supported bimetallic catalyst Download PDF

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CN107089899B
CN107089899B CN201710296122.3A CN201710296122A CN107089899B CN 107089899 B CN107089899 B CN 107089899B CN 201710296122 A CN201710296122 A CN 201710296122A CN 107089899 B CN107089899 B CN 107089899B
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octanol
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CN107089899A (en
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冯传密
马啸
都荣强
孙荣钦
陈为超
马慧娟
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Shandong Nhu Pharmaceutical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/892—Nickel and noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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    • C07C2/24—Catalytic processes with metals

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Abstract

The invention provides a method for preparing n-octanol by adopting a supported bimetallic catalyst, which comprises the following steps: step 1) adding an organic solvent, water and a supported catalyst, introducing 1, 3-butadiene, and reacting at a certain temperature; and 2) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, and introducing hydrogen to prepare the n-octanol. The method for preparing the n-octanol has high yield; the yield is 87.6-95.6%; the catalyst is filtered and applied mechanically, the reaction is simple and convenient, and the catalyst is not easy to inactivate compared with a homogeneous catalyst. The invention can be used as a more effective alternative method for preparing n-octanol. The reaction is realized by a one-pot method, the catalyst is filtered after the reaction is finished and directly reacts again, the inactivation phenomenon is not seen after the catalyst is continuously used for 50 times, and the reaction yield is only reduced by 1.5-2 percentage points when the catalyst is used for 50 times; the n-octanol is prepared by a one-pot method, and the reaction route is short.

Description

Method for preparing n-octanol by adopting supported bimetallic catalyst
Technical Field
The invention relates to a method for preparing n-octanol by using a supported bimetallic catalyst, belonging to the technical field of chemical synthesis.
Background
N-octanol has dry, sweet and sharp lipid wax fragrance, citrus, orange peel and rose-like smell, like the cream-like base fragrance of radix sileris, and has no long-lasting fragrance. And has oil and fat fruity flavor, sweet and slightly grass flavor. The method is mainly used for producing plasticizers, extracting agents and stabilizing agents. Octanol is also used as a fragrance per se, blended with floral essences such as rose, lily, etc., as a soap fragrance. The product is edible spice which is specified as allowed in GB2760-86 of China. The method is mainly used for preparing coconut, pineapple, peach, chocolate and citrus essences.
The current n-octanol process route is four processes of a Ziegler method, n-octanoic acid hydrogenation, carbonyl synthesis and telomerization hydration, and is concretely described as follows.
The Ziegler method: ethylene is used as a raw material, alkyl aluminum is used as a catalyst, and high-carbon alcohol is produced through oxidation and hydrolysis. The process route is used for producing high-carbon alcohol by domestic Jilin chemical industry, and high-carbon single alcohol and mixed alcohol are produced by foreign Huawang companies. The resulting product is a mixed alcohol, typically used for surfactants. The product has more categories, low n-octanol content, complex separation and lower purity.
N-octanoic acid hydrogenation process: coconut oil is rich in n-caprylic acid (about 10 percent), and under the conditions of high temperature and high pressure, the cobalt catalytic hydrogenation reaction is utilized to produce n-caprylic alcohol; the process is subject to the supply of raw materials, and manufacturers are concentrated in southeast Asia, where Cochinchina Malaysia and Thailand Inc. use the coconut oil hydrogenation process. The process not only needs a complex process for extracting the caprylic acid, but also needs high temperature (200-.
And (3) oxo synthesis: the process uses alpha-heptene and mixed gas to carry out hydroformylation reaction under the catalysis of noble metal rhodium, and an intermediate octanal is hydrogenated to prepare n-octanol, wherein the core of the process is an alpha-heptene source. In the last 50 th century, the alpha-olefin is prepared by paraffin dehydrogenation, so that the higher cost is eliminated; south Africa is forbidden to be transported by petroleum at the same stage, energy crisis forces south Africa to accelerate coal-to-oil process development, the coal-to-oil process production is realized after 5 years of development, alpha-heptene can be obtained through rectification and purification, and the alpha-heptene process which is the most competitive one in the world at present. The process uses longer carbon chain olefins and a rhodium catalyst to produce isoolefins and 2-methylheptanal byproduct.
Telomerization and hydration: in 1972, Jiro Tsuji reported that the dimerization hydration reaction of butadiene based on homogeneous metal palladium catalysis provided a simple process route for n-octanol industrialization (Accounts of Chemical Research,1973, 6, 8-15), and made a pioneering explanation for the mechanism of the reaction, which goes through a sigma-pi complex, with water as an affinity reagent further participating in the reductive elimination process of palladium metal. The continuous application effect of the process is poor at present, and a large amount of water-soluble auxiliary agent is required to be used.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a method for preparing n-octanol by adopting a supported bimetallic catalyst, which aims to realize the following purposes:
(1) the method for preparing the n-octanol has high yield;
(2) the continuous application of the catalyst is realized, and the catalyst is not easy to inactivate after being applied for 50 times.
The reaction formula of the invention is as follows:
Figure 707588DEST_PATH_IMAGE001
in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing n-octanol by adopting a supported bimetallic catalyst comprises the following steps:
step 1) adding an organic solvent, water and a supported catalyst, introducing 1, 3-butadiene, and reacting at a certain temperature;
and 2) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, and introducing hydrogen to prepare the n-octanol.
The active component of the supported catalyst in the step 1) is XaNibX is one of Pd, Fe, Sn, Cu, Co and Rh; x is preferably Pd, Sn, Cu, Co, Rh, and the most preferred metal combination is Rh-Ni.
The mass ratio of the X to the Ni in the step 1) is a: b = 1: 1 to 2. The preferred ratio is 1: (1-1.2), and the most preferable ratio is: 1: 2.
the carrier of the supported catalyst in the step 1) is one of activated carbon, molecular sieve, alumina, silicon dioxide and hydrotalcite; most preferably, the support is activated carbon.
The molar ratio of 1, 3-butadiene to water in step 1) is 1: (0.5 to 4); the preferred ratio is 1: (0.5 to 1); the most preferred ratio is 1: 1;
the reaction temperature in the step 1) is 40-100 ℃, and the preferable temperature is 60-80 ℃; most preferably the temperature is 60 ℃.
The mass ratio of the supported catalyst to the 1, 3-butadiene in the step 1) is (0.1-2.0%); the preferable proportion is 0.5% -1.0%; the most preferred ratio is 0.5%.
The organic solvent in the step 1) is tetrahydrofuran,N,N-one of dimethylformamide, 1, 4-dioxane, dimethyl sulfoxide, acetonitrile; the most preferred solvent is tetrahydrofuran.
Step 2), introducing hydrogen at the pressure of 0.1-10 MPa; the preferable pressure is 1-2 MPa.
And 2) preparing n-octanol, finishing the reaction when the GC content of the 2, 7-octadiene-1-alcohol is detected to be less than or equal to 0.1%, and cooling the water to room temperature.
The method for preparing the n-octanol has high yield; the yield is 87.6-95.6%; by adopting the preferable scheme, the n-octanol is prepared, and the yield reaches 92-95.6%.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method for preparing the n-octanol has high yield; the yield is 87.6-95.6%;
(2) the catalyst is filtered and applied mechanically, the reaction is simple and convenient, and the catalyst is not easy to inactivate compared with a homogeneous catalyst. The invention can be used as a more effective alternative method for preparing n-octanol. The reaction is realized by a one-pot method, the catalyst is filtered after the reaction is finished and directly reacts again, the inactivation phenomenon is not seen after the catalyst is continuously used for 50 times, and the reaction yield is only reduced by 1.5-2 percentage points when the catalyst is used for 50 times;
(3) the n-octanol is prepared by a one-pot method, and the reaction route is short.
Detailed Description
Example 1A method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of tetrahydrofuran was added to the autoclave, and 18.0g (1.0mol) of water and 1.1g of catalyst 5% Pd-10% Ni/activated carbon were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 10 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, and finishing the reaction; introducing hydrogen at the pressure of 0.1MPa, reacting for 2 hours until the GC content of the intermediate 2, 7-octadiene is less than or equal to 0.1 percent, and cooling to room temperature after the reaction is finished;
(4) 118.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 90.8 percent.
Example 2 method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of tetrahydrofuran was added to the autoclave, and 36.0g (2.0mol) of water and 0.1g of 10% Pd-10% Ni/molecular sieve catalyst were added thereto;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 40 ℃ for reaction for 12 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 1 hour under the pressure of 1MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the water to room temperature;
(4) 121.2g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 93.1 percent.
Example 3A method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of N, N-dimethylformamide, 36.0g (2.0mol) of water and 2.1g of 10% Fe-10% Ni/alumina catalyst were added to an autoclave;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 80 ℃ for reacting for 8 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 0.5 hour under the pressure of 10MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the water to room temperature;
(4) 113.9g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 87.6 percent.
Example 4A method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of 1, 4-dioxane is added into an autoclave, 9.0g (0.5mol) of water and 1.0g of 10% Sn-10% Ni/hydrotalcite catalyst are added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 100 ℃ for reaction for 20 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 0.5 hour under the pressure of 10MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the water to room temperature;
(4) 69.2g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 92.0 percent.
Example 5A method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of dimethyl sulfoxide was added to an autoclave, 18.0g (1.0mol) of water and 1.1g of catalyst, Cu 10% to Ni 10% to silica were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 20 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 2 hours at the pressure of 1MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the water to room temperature;
(4) 120.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 92.3 percent.
Example 6A method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of acetonitrile is added into an autoclave, 72.0g (4.0mol) of water and 0.5g of catalyst 10% Co-10% Ni/active carbon are added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 15 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 2 hours at the pressure of 0.5MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the introduced water to room temperature;
(4) 122.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 93.9 percent.
Example 7A method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of tetrahydrofuran was added to the autoclave, 18.0g (1.0mol) of water and 0.5g of catalyst 10% Rh-10% Ni/activated carbon were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 15 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 2 hours at the pressure of 1.5MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the introduced water to room temperature;
(4) 122.5g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 94.2 percent.
Example 8A method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of tetrahydrofuran was added to the autoclave, 18.0g (1.0mol) of water and 0.5g of catalyst 5% Rh-10% Ni/activated carbon were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 25 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 5 hours at the pressure of 1.5MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the introduced water to room temperature;
(4) 123.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 94.7 percent.
Example 9A method for preparing n-octanol Using Supported bimetallic catalyst
The method comprises the following steps:
(1) 100 mL of tetrahydrofuran was added to the autoclave, and 18.0g (1.0mol) of water and 0.5g of 5% Rh-5% Ni/molecular sieve catalyst were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 12 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 2 hours at the pressure of 1.0 MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the introduced water to room temperature;
(4) 121.2g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 95.6 percent.
The results of using the catalyst described in example 9 with the same process parameters as in example 9 for 50 times are shown in Table 1.
Figure 425008DEST_PATH_IMAGE002
Rh, Ni, Co, Pt, Pd were used alone as active ingredients of the catalyst, and supported on an activated carbon support, and reactions for catalytically preparing n-octanol were performed, respectively, as comparative experiments, and specifically, see the following examples.
Example 10
(1) 100 mL of tetrahydrofuran was charged into the autoclave, and 18.0g (1.0mol) of water and 0.5g of 5% Rh/activated carbon as a catalyst were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 48 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 5 hours at the pressure of 1.5MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the introduced water to room temperature;
(4) 123.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 43.2 percent.
Example 11
(1) 100 mL of tetrahydrofuran was charged into an autoclave, and 18.0g (1.0mol) of water and 0.5g of 5% Ni/activated carbon as a catalyst were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, heating to 60 ℃ and reacting for 78 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 5 hours at the pressure of 1.5MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the introduced water to room temperature;
(4) 123.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 21.2 percent.
Example 12
(1) 100 mL of tetrahydrofuran was added to the autoclave, 18.0g (1.0mol) of water and 0.5g of catalyst 5% Co/activated carbon were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, heating to 60 ℃ and reacting for 56 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 35 hours at the pressure of 10MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the water to room temperature;
(4) 123.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 5.3 percent.
Example 13
(1) 100 mL of tetrahydrofuran was added to the autoclave, 18.0g (1.0mol) of water and 0.5g of 5% Pt/active carbon as a catalyst were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 50 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 40 hours at the pressure of 10MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the water to room temperature;
(4) 123.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 12.3 percent.
Example 14
(1) 100 mL of tetrahydrofuran was charged into an autoclave, and 18.0g (1.0mol) of water and 0.5g of 5% Pd/activated carbon as a catalyst were added;
(2) introducing 108.0g (2.0mol) of 1, 3-butadiene, and heating to 60 ℃ for reaction for 48 hours;
(3) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, finishing the reaction, introducing hydrogen for 5 hours at the pressure of 10MPa, detecting that the GC content of the 2, 7-octadiene-1-ol is less than or equal to 0.1 percent, finishing the reaction, and cooling the water to room temperature;
(4) 123.1g of n-octanol is separated by rectification (30 Pa, the kettle temperature is 80 ℃, the tower top temperature is 45 ℃, and GC is more than or equal to 99.0 percent), and the yield is 40.8 percent.
Unless otherwise specified, the proportions in the present invention are mass proportions, and the percentages are mass percentages.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. A method for preparing n-octanol by adopting a supported bimetallic catalyst is characterized by comprising the following steps:
step 1) adding an organic solvent, water and a supported catalyst, introducing 1, 3-butadiene, and reacting at a certain temperature;
step 2) detecting that the GC content of the 1, 3-butadiene is less than or equal to 0.3 percent, and introducing hydrogen to prepare n-octanol;
the active component of the supported catalyst in the step 1) is XaNibX is one of Pd, Fe, Sn, Cu, Co and Rh; the mass ratio of the X to the Ni in the step 1) is a: b = 1: 1-2;
the carrier of the supported catalyst in the step 1) is one of activated carbon, molecular sieve, alumina, silicon dioxide and hydrotalcite.
2. The method for preparing n-octanol using supported bimetallic catalyst according to claim 1, wherein the molar ratio of 1, 3-butadiene to water in step 1) is 1: (0.5 to 4).
3. The method for preparing n-octanol using supported bimetallic catalyst as claimed in claim 1, wherein the temperature of reaction in step 1) is 40-100 ℃.
4. The method for preparing n-octanol by using supported bimetallic catalyst as claimed in claim 1, wherein the mass ratio of supported catalyst to 1,3 butadiene in step 1) is 0.1-2.0%.
5. The method for preparing n-octanol using supported bimetallic catalyst as claimed in claim 1, wherein the organic solvent in step 1) is tetrahydrofuran、N,N-one of dimethylformamide, 1, 4-dioxane, dimethyl sulfoxide and acetonitrile.
6. The method for preparing n-octanol using supported bimetallic catalyst as claimed in claim 1, wherein step 2) is performed by introducing hydrogen at a pressure of 0.1-10 MPa.
7. The method for preparing n-octanol using supported bimetallic catalyst as claimed in claim 1, wherein step 2) is performed to prepare n-octanol, and the reaction is terminated when GC content of 2, 7-octadien-1-ol is detected to be less than or equal to 0.1%, and water is cooled to room temperature.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417079A (en) * 1981-02-16 1983-11-22 Kuraray Company, Limited Process for producing normal-octanol
CN102773097A (en) * 2011-05-13 2012-11-14 华东理工大学 Preparation of loaded bimetallic nano-catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4417079A (en) * 1981-02-16 1983-11-22 Kuraray Company, Limited Process for producing normal-octanol
CN102773097A (en) * 2011-05-13 2012-11-14 华东理工大学 Preparation of loaded bimetallic nano-catalyst

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