CN112547095A - Catalyst for preparing cis-pinane by alpha-pinene hydrogenation and preparation method and application thereof - Google Patents

Catalyst for preparing cis-pinane by alpha-pinene hydrogenation and preparation method and application thereof Download PDF

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CN112547095A
CN112547095A CN202011260677.0A CN202011260677A CN112547095A CN 112547095 A CN112547095 A CN 112547095A CN 202011260677 A CN202011260677 A CN 202011260677A CN 112547095 A CN112547095 A CN 112547095A
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pinene
catalyst
alpha
pinane
reaction
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CN112547095B (en
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陈芬儿
黄华山
程荡
姜梅芬
刘敏杰
王路路
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Fudan University
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    • 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
    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
    • B01J31/0207—Aldehydes or acetals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2525/00—Catalysts of the Raney type
    • C07C2525/02—Raney nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

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Abstract

The invention relates to a catalyst for preparing cis-pinane by alpha-pinene hydrogenation, a preparation method and application thereof, wherein the catalyst is a skeleton nickel catalyst and is composed of nickel-aluminum-molybdenum ternary elements, the weight ratio of molybdenum to nickel is 1-12%, and the weight ratio of molybdenum to aluminum is 1-15%. The preparation method comprises the following steps: firstly, treating nickel-aluminum alloy particles or fine powder containing a doping element molybdenum by using inorganic alkali liquor at 10-80 ℃ for 0.5-3 hours, then heating to 80-105 ℃, continuing to treat for 1-12 hours, filtering out solids, washing the solids to be neutral, and then placing the solids in alcohol at-30 ℃ for storage. The invention discloses a method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation by using a formalin-modified Raney nickel catalyst. The catalyst of the invention has simple preparation, the substrate alpha-pinene can be converted quantitatively, the yield of the cis-pinane is more than 95 percent, the selectivity is more than 95 percent, and the catalyst has good stability and can be repeatedly used.

Description

Catalyst for preparing cis-pinane by alpha-pinene hydrogenation and preparation method and application thereof
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a catalyst for preparing cis-pinane by hydrogenating alpha-pinene, and a preparation method and application thereof.
Background
Alpha-pinene is the main component of turpentine oil, and pinane can be prepared by catalytic hydrogenation. Pinane is an important intermediate in the perfume and medical industries, and since the cis-pinane has much higher reactivity than the trans-form, pinane used in the industry is mainly required to have a cis-structure.
The remaining soldiers et al (Guangzhou chemistry, 1999,21:23-27) and Irina et al (appl. Catal. A Gen.,2009,356,216-224) all reported Pd/C catalyzed hydrogenation of alpha-pinene with substrate conversion up to 99%, but only 80.1% selectivity, which is too low. The remaining soldiers (Guangzhou chemistry 1999,21:23-27) use CuCl2After the Pd/C catalyst is modified, the selectivity of the cis-pinane is increased to 93.1 percent, but the substrate conversion rate is reduced to 63.3 percent in the same reaction time.
Jenke et al (J.Organomet. chem.,1991,405: 383-391) describe the use of a soluble chiral catalyst HRu2(CO)4And HRu3(CO)9The method for catalyzing hydrogenation of alpha-pinene has cis-pinane selectivity approaching 100% in 15 hr reaction at 90 deg.c and 5MPa pressure. The disadvantages of this method are harsh reaction conditions, long reaction time, expensive catalyst and high cost.
The use of supported Ru/gamma-Al is described in U.S. Pat. Nos. 5132270, 3277208, 4310714 and EP0472852B12O3The process of catalyzing alpha-pinene hydrogenation by the catalyst has the reaction performed under mild conditions, and the cis-pinane content in the product reaches 95-97%. Chinese patent CN105330505 discloses the use of rhodium catalyst [ Rh (COD) Cl]2The cis-pinane selectivity is greater than 95% in the procedure of catalyzing the reaction. Although the noble metal catalysts have high selectivity in catalyzing the hydrogenation reaction of alpha-pinene, the practical industrial application is limited by the expensive price of the noble metal catalysts.
Ren et Al (Chin.J.Inorg.chem.,2007,23:1021-2O3The process for catalyzing alpha-pinene hydrogenation reaction by the catalyst has the advantages that the conversion rate of a substrate is 47-97.7% after 6.5 hours of reaction, and the cis-pinane selectivity is 63-91%. The disadvantage of this process is the low selectivity of the cis isomer.
The U.S. Pat. No. 4, 4018842 poisons the surface of nickel catalyst partially to prepare Ni-Zr/diatomite catalyst, which catalyzes the hydrogenation reaction of alpha-pinene at 30 deg.C under 1.4MPa for 19 hours, and the cis-pinane selectivity in the product is 95%. The disadvantage of this process is the excessively long reaction times. Ko Sunhua et Al (Ind. Eng. chem. Res.,1993,32: 1579-1587.; Ind. Eng. chem. Res.,1995,34:457-467) report Ni-P/gamma-Al2O3And Ni-P/nylon-66 as catalyst to obtain cis-pinane in high selectivity. Chinese invention patents CN 102125864B and CN 104003835B respectively use P or B modified nickel catalyst to prepare Ni-B-molecular sieve and Ni-P-SiO2Amorphous catalyst, Chinese patent application CN 102205245A, crystalline nano nickel is loaded on magnetic Fe3O4Both on powder and in chinese patent application CN 1262263a, the nickel-skeletal catalyst modified with transition metal elements of I B, II B or VIII group, obtained more than 95% of cis-isomers. Polish patent PL127559B1 discloses a method for catalyzing pinene hydrogenation by using a supported nickel/kieselguhr catalyst with a small amount of Mg, B and Pd as auxiliaries, and the content of cis-pinane can reach 99%.
The common defects of the methods are that the preparation process of the catalyst is complex, the stability is poor, and the catalyst is difficult to be repeatedly used. Therefore, research and development of a novel catalyst which can be recycled and has better performance and used for preparing the cis-pinane by the catalytic hydrogenation of the alpha-pinene become a problem to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a catalyst for preparing cis-pinane by catalytic hydrogenation of alpha-pinene and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a catalyst for preparing cis-pinane by hydrogenation of α -pinene, wherein the catalyst is a skeletal nickel catalyst, and nickel, aluminum and molybdenum elements are used as raw materials;
in the raw materials, molybdenum exists in a form of doped elements, the weight ratio of molybdenum to nickel is 1-12%, and the weight ratio of molybdenum to aluminum is 1-15%.
As an optional embodiment, the weight ratio of molybdenum to nickel in the raw material is 1-12%.
As an optional embodiment, the weight ratio of molybdenum to nickel in the raw material is 1-7%.
As an optional embodiment, the weight ratio of molybdenum to aluminum in the raw material is 1-15%.
As an optional embodiment, the weight ratio of molybdenum to aluminum in the raw material is 1-6%.
A second aspect of the present invention provides a process for preparing a catalyst according to the first aspect of the present invention, comprising the steps of:
step (1): slowly adding nickel-aluminum alloy particles or fine powder containing a doping element molybdenum into an inorganic alkali liquor, and controlling the temperature of the inorganic alkali liquor within the range of 10-80 ℃ to react for 0.5-3 hours after the addition is finished;
step (2): raising the temperature of the inorganic alkali liquor in the step (1) to 80-105 ℃, and reacting for 1-12 hours in a heat preservation manner to obtain a reaction mixture;
and (3): and (3) filtering out a solid in the reaction mixture in the step (2), washing the solid to be neutral by using water, and storing the solid in alcohol at the temperature of-30 ℃.
As an alternative embodiment, the inorganic alkali solution is an aqueous solution of NaOH or an aqueous solution of KOH.
As an optional embodiment, the concentration of the NaOH aqueous solution or the KOH aqueous solution is 10 to 50% by mass; preferably, the mass percentage concentration of the NaOH aqueous solution or the KOH aqueous solution is 15-45%, and the reaction effect is better.
As an optional implementation mode, the particle size of the nickel-aluminum alloy particles or fine powder containing the doping element molybdenum is more than 100 meshes, and the reaction effect is better.
The third aspect of the invention provides a method for preparing cis-pinane by catalyzing hydrogenation of alpha-pinene, wherein the method comprises the following steps:
the catalyst of the first aspect of the invention is used for catalyzing alpha-pinene hydrogenation to prepare cis-pinane.
As an alternative embodiment, the method according to the third aspect of the present invention comprises the steps of:
step (1): placing alpha-pinene and the skeletal nickel catalyst into a reaction kettle;
step (2): vacuumizing for 10 minutes under the gauge pressure of 0.01-0.09 MPa, replacing for 3-4 times under the pressure of 0.1-0.5 MPa by using nitrogen, replacing for 3-6 times under the pressure of 0.1-0.5 MPa by using hydrogen, detecting leakage, and confirming that the reaction kettle is well sealed;
and (3): and opening a hydrogen gas inlet valve, adjusting the pressure in the reaction kettle to be 0.2-6 MPa, raising the temperature in the reaction kettle to 30-70 ℃, adjusting the stirring speed to be 500-1000 r/min, and reacting for 2-8 hours.
As an optional embodiment, in the step (1), the skeletal nickel catalyst is used in an amount of 0.5 to 10% by weight of the α -pinene.
As an alternative embodiment, in step (1), the α -pinene is present in a solvent-free form.
As an alternative embodiment, in step (1), the α -pinene is present in the form of a solution dissolved in an organic solvent; the organic solvent is C1-C4 alkanol, and the C1-C4 alkanol is any one of methanol, ethanol, ethylene glycol, 1-propanol, 2-propanol, 1, 2-propanediol, 1, 3-propanediol and 1-butanol; preferably, the organic solvent is C2-C4 alkanol, so that the reaction effect is better and the reaction time is shorter.
As an optional implementation mode, in the step (3), the pressure of the hydrogen in the reaction kettle is controlled to be 1.5-4.5 MPa, and the effect is better.
The fourth aspect of the invention provides a method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation by using a formalin-modified Raney nickel catalyst, which comprises the following steps:
step (1): using formalin to modify a Raney nickel catalyst to obtain a modified Raney nickel catalyst;
step (2): placing alpha-pinene and the modified Raney nickel catalyst into a reaction kettle;
and (3): vacuumizing for 10 minutes under the gauge pressure of 0.01-0.09 MPa, replacing for 3-4 times under the pressure of 0.1-0.5 MPa by using nitrogen, replacing for 3-6 times under the pressure of 0.1-0.5 MPa by using hydrogen, detecting leakage, and confirming that the reaction kettle is well sealed;
and (4): and opening a hydrogen gas inlet valve, adjusting the pressure in the reaction kettle to be 0.1-6 MPa, raising the temperature in the reaction kettle to 35-90 ℃, adjusting the stirring speed to be 500-1000 r/min, and reacting for 4-10 hours.
As an alternative embodiment, the step (1) "using formalin modified raney nickel catalyst" specifically includes the following steps:
step (a): dispersing Raney nickel in a liquid dispersion medium, adding a formalin solution which is 0.5-30% of the weight of the Raney nickel, and stirring for 10 minutes to 3 hours at 10-75 ℃ under the protection of inert gas to obtain a mixed solution;
step (b): and (c) filtering out solids in the mixed solution in the step (a), washing the mixed solution for several times by using deionized water to obtain the modified Raney nickel catalyst, and storing the modified Raney nickel catalyst in water at the temperature of 5-35 ℃.
As an optional embodiment, the particle size of the Raney nickel is more than 20 meshes, and the Raney nickel with more than 60 meshes is used, so that the modification effect is better.
As an optional implementation mode, the weight ratio of the Raney nickel to the liquid dispersion medium is 10-65%, and the weight ratio of the Raney nickel to the liquid dispersion medium is controlled within the range of 25-60%, so that the modification effect is better.
As an alternative embodiment, the liquid dispersion medium is water, or a single organic solvent, or a mixed solution of two or more of the foregoing liquids. The liquid dispersion medium used may be a mixed solution composed of water and one or more organic solvents in any mass ratio. For example, the liquid dispersion medium may be a mixed solution composed of water and methanol in any mass ratio, or the liquid dispersion medium may be a mixed solution composed of water and ethanol in any mass ratio, or the liquid dispersion medium may be a mixed solution composed of ethanol and ethylene glycol in any mass ratio.
As an alternative embodiment, the organic solvent is an alkanol having a carbon number of from 1 to 4, such as methanol, ethanol, ethylene glycol, 1-propanol, 2-propanol, 1, 2-propanediol, 1, 3-propanediol, 1-butanol, and the like.
As an alternative embodiment, in the step (a), the inert gas is one of nitrogen, argon, helium and neon.
As an optional implementation manner, in the step (a), the modification temperature condition is controlled within a range of 20 to 50 ℃ more preferably.
As an optional embodiment, in the step (2), the modified raney nickel catalyst is used in an amount of 0.7 to 8% by weight of the α -pinene.
As an alternative embodiment, in step (2), the α -pinene is present in the form of a solution dissolved in an organic solvent; the organic solvent is C1-C4 alkanol, and the C1-C4 alkanol is any one of methanol, ethanol, ethylene glycol, 1-propanol, 2-propanol, 1, 2-propanediol, 1, 3-propanediol and 1-butanol.
As an alternative embodiment, in step (2), the α -pinene may exist in a solvent-free form, and the reaction speed is faster and the selectivity is better.
As an optional implementation mode, in the step (4), the pressure of the hydrogen in the reaction kettle is controlled to be 2-4 MPa, and the effect is better.
The invention also provides the application of the skeletal nickel catalyst as a catalyst in the reaction of preparing cis-pinane by hydrogenation of alpha-pinene.
Furthermore, the skeletal nickel catalyst takes nickel, aluminum and molybdenum elements as raw materials;
in the raw materials, molybdenum exists in a form of doped elements, the weight ratio of molybdenum to nickel is 1-12%, and the weight ratio of molybdenum to aluminum is 1-15%.
The invention also provides an application of the formalin modified Raney nickel catalyst as a catalyst in a reaction for preparing cis-pinane by hydrogenation of alpha-pinene.
The catalyst is adopted to catalyze the alpha-pinene to prepare the cis-pinane through hydrogenation, the reaction substrate alpha-pinene can be quantitatively converted, the yield of the cis-pinane is more than 95 percent, the selectivity is more than 95 percent, the catalyst has high stability, can be repeatedly used for a plurality of times without inactivation, the reaction condition is mild, the operation is simple and convenient, the cost is low, and the catalyst is suitable for industrial production.
Detailed Description
In order to explain technical contents, structural features, and objects and effects of the technical means in detail, the following detailed description is given with reference to specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments.
It should be noted that the test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
1. Preparation of molybdenum-containing skeletal nickel catalyst
Weighing 10g of sodium hydroxide, dissolving the sodium hydroxide by 90g of deionized water, adding 10g of nickel-aluminum-molybdenum (Ni-Al-Mo) ternary alloy powder with the granularity of 100 meshes, firstly reacting for 1 hour at 50 ℃, then preserving the heat at 80 ℃ for reacting for 7 hours, then filtering out solids in the ternary alloy powder, washing the solids to be neutral by water to prepare a molybdenum-containing skeleton nickel catalyst, and placing the molybdenum-containing skeleton nickel catalyst in alcohol at 15 ℃.
In the Ni-Al-Mo ternary alloy powder, the weight ratio of Mo to Ni is 2%, and the weight ratio of Mo to Al is 2%.
2. Catalytic hydrogenation reaction of alpha-pinene
1g of the molybdenum-containing skeletal nickel catalyst prepared in the embodiment and 100g of alpha-pinene are placed in a reaction kettle, vacuum pumping is carried out for 10 minutes under gauge pressure of 0.09MPa, nitrogen is used for replacing for three times under 0.5MPa, hydrogen is used for replacing for three times under 0.5MPa, leakage detection is carried out, and the reaction kettle is confirmed to be well sealed. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, stirring and reacting for 12 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 95.3%, and the yield is 95.3%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 98.3%, the selectivity of cis-pinane was 95.1%, and the yield was 93.5% in the same reaction time.
Example 2 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
1. Preparation of molybdenum-containing skeletal nickel catalyst
Weighing 30g of sodium hydroxide, dissolving the sodium hydroxide by using 70g of deionized water, adding 10g of nickel-aluminum-molybdenum (Ni-Al-Mo) ternary alloy powder with the granularity of 100 meshes, firstly reacting for 1 hour at 50 ℃, then preserving the heat at 80 ℃ for reacting for 7 hours, then filtering out solids in the solution, washing the solids with water to be neutral to prepare a molybdenum-containing skeleton nickel catalyst, and placing the molybdenum-containing skeleton nickel catalyst in alcohol at 15 ℃ for storage.
In the Ni-Al-Mo ternary alloy powder, the weight ratio of Mo to Ni is 2%, and the weight ratio of Mo to Al is 2%.
2. Catalytic hydrogenation reaction of alpha-pinene
1g of the molybdenum-containing skeletal nickel catalyst prepared in the embodiment and 100g of alpha-pinene are placed in a reaction kettle, vacuum pumping is carried out for 10 minutes under gauge pressure of 0.09MPa, nitrogen is used for replacing for three times under 0.5MPa, hydrogen is used for replacing for three times under 0.5MPa, leakage detection is carried out, and the reaction kettle is confirmed to be well sealed. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, and stirring for reaction for 7 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 95.8%, and the yield is 95.8%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 99.3%, the selectivity of cis-pinane was 95.3%, and the yield was 94.6% in the same reaction time.
Example 3 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
1. Preparation of molybdenum-containing skeletal nickel catalyst
Weighing 30g of sodium hydroxide, dissolving the sodium hydroxide by using 70g of deionized water, adding 10g of nickel-aluminum-molybdenum (Ni-Al-Mo) ternary alloy powder with the granularity of 300 meshes, firstly reacting for 1 hour at 50 ℃, then preserving the heat at 80 ℃ for reacting for 7 hours, then filtering out solids in the solution, washing the solids with water to be neutral to prepare a molybdenum-containing skeleton nickel catalyst, and placing the molybdenum-containing skeleton nickel catalyst in alcohol at 15 ℃ for storage.
In the Ni-Al-Mo ternary alloy powder, the weight ratio of Mo to Ni is 2%, and the weight ratio of Mo to Al is 2%.
2. Catalytic hydrogenation reaction of alpha-pinene
1g of the molybdenum-containing skeletal nickel catalyst prepared in the embodiment and 100g of alpha-pinene are placed in a reaction kettle, vacuum pumping is carried out for 10 minutes under gauge pressure of 0.09MPa, nitrogen is used for replacing for three times under 0.5MPa, hydrogen is used for replacing for three times under 0.5MPa, leakage detection is carried out, and the reaction kettle is confirmed to be well sealed. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, and stirring for 5 hours to react, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 96.7%, and the yield is 96.7%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 99.6%, the selectivity of cis-pinane was 95.5%, and the yield was 95.1% in the same reaction time.
Example 4 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
1. Preparation of molybdenum-containing skeletal nickel catalyst
Weighing 30g of sodium hydroxide, dissolving the sodium hydroxide by using 70g of deionized water, adding 10g of nickel-aluminum-molybdenum (Ni-Al-Mo) ternary alloy powder with the granularity of 100 meshes, firstly reacting for 1 hour at 50 ℃, then preserving the heat at 98 ℃ for reacting for 7 hours, then filtering out solids in the solution, washing the solids with water to be neutral to prepare a molybdenum-containing skeleton nickel catalyst, and placing the molybdenum-containing skeleton nickel catalyst in alcohol at 15 ℃.
In the Ni-Al-Mo ternary alloy powder, the weight ratio of Mo to Ni is 2%, and the weight ratio of Mo to Al is 2%.
2. Catalytic hydrogenation reaction of alpha-pinene
1g of the molybdenum-containing skeletal nickel catalyst prepared in the embodiment and 100g of alpha-pinene are placed in a reaction kettle, vacuum pumping is carried out for 10 minutes under gauge pressure of 0.09MPa, nitrogen is used for replacing for three times under 0.5MPa, hydrogen is used for replacing for three times under 0.5MPa, leakage detection is carried out, and the reaction kettle is confirmed to be well sealed. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, and stirring for reaction for 7 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 95.9%, and the yield is 95.9%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 99.4%, the selectivity of cis-pinene was 95.4%, and the yield was 94.8% in the same reaction time.
Example 5 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
1. Preparation of molybdenum-containing skeletal nickel catalyst
Weighing 30g of sodium hydroxide, dissolving the sodium hydroxide by using 70g of deionized water, adding 10g of nickel-aluminum-molybdenum (Ni-Al-Mo) ternary alloy powder with the granularity of 100 meshes, firstly reacting for 1 hour at 50 ℃, then preserving the heat at 98 ℃ for reacting for 7 hours, then filtering out solids in the solution, washing the solids with water to be neutral to prepare a molybdenum-containing skeleton nickel catalyst, and placing the molybdenum-containing skeleton nickel catalyst in alcohol at 15 ℃.
In the Ni-Al-Mo ternary alloy powder, the weight ratio of Mo to Ni is 5%, and the weight ratio of Mo to Al is 5%.
2. Catalytic hydrogenation reaction of alpha-pinene
1g of the molybdenum-containing skeletal nickel catalyst prepared in the embodiment and 100g of alpha-pinene are placed in a reaction kettle, vacuum pumping is carried out for 10 minutes under gauge pressure of 0.09MPa, nitrogen is used for replacing for three times under 0.5MPa, hydrogen is used for replacing for three times under 0.5MPa, leakage detection is carried out, and the reaction kettle is confirmed to be well sealed. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, and stirring for reaction for 7 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 96.2%, and the yield is 96.2%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 99.6%, the selectivity of cis-pinane was 95.5%, and the yield was 95.1% in the same reaction time.
Example 6 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
1. Preparation of molybdenum-containing skeletal nickel catalyst
Weighing 30g of sodium hydroxide, dissolving the sodium hydroxide by using 70g of deionized water, adding 10g of nickel-aluminum-molybdenum (Ni-Al-Mo) ternary alloy powder with the granularity of 100 meshes, firstly reacting for 2 hours at 35 ℃, then preserving the heat at 80 ℃ for reacting for 7 hours, then filtering out solids in the solution, washing the solids with water to be neutral to prepare a molybdenum-containing skeleton nickel catalyst, and placing the molybdenum-containing skeleton nickel catalyst in alcohol at 15 ℃ for storage.
In the Ni-Al-Mo ternary alloy powder, the weight ratio of Mo to Ni is 2%, and the weight ratio of Mo to Al is 2%.
2. Catalytic hydrogenation reaction of alpha-pinene
(1) 2.5g of the molybdenum-containing skeletal nickel catalyst prepared in the embodiment and 100g of alpha-pinene are placed in a reaction kettle, vacuum pumping is carried out for 10 minutes under the gauge pressure of 0.09MPa, nitrogen is used for replacing for three times under the pressure of 0.5MPa, hydrogen is used for replacing for three times under the pressure of 0.5MPa, and the leak detection is carried out to confirm that the reaction kettle is well sealed. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, and stirring for reaction for 7 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 95.4%, and the yield is 95.4%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction using the recovered catalyst was repeated, and it was found that after the catalyst was repeatedly used 10 times, under the same experiment and operation conditions of this example, the conversion rate of α -pinene was 98.5%, the selectivity of cis-pinane was 95.1%, and the yield was 93.7% in the same reaction time.
Example 7 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
2.5g of the molybdenum-containing skeletal nickel catalyst prepared in example 6, 100g of alpha-pinene and 10mL of methanol were placed in a reaction vessel, vacuum was applied for 10 minutes at a gauge pressure of 0.09MPa, nitrogen was used for three times at 0.5MPa, hydrogen was used for three times at 0.5MPa, and the vessel was checked for leaks to confirm that the vessel was sealed well. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, stirring and reacting for 8 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 95%, and the yield is 95%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 98.1%, the cis-pinane selectivity was 95%, and the yield was 93.2% in the same reaction time.
Example 8 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
2.5g of the molybdenum-containing skeletal nickel catalyst prepared in example 6, 100g of alpha-pinene and 10mL of ethanol were placed in a reaction kettle, vacuum was applied for 10 minutes at a gauge pressure of 0.09MPa, nitrogen was used for replacement three times at 0.5MPa, and hydrogen was used for replacement three times at 0.5MPa, and leak detection was performed to confirm that the reaction kettle was sealed well. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, and stirring for reacting for 8 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 95.2%, and the yield is 95.2%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 98.3%, the selectivity of cis-pinene was 95%, and the yield was 93.4% in the same reaction time.
Example 9 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
2.5g of the molybdenum-containing skeletal nickel catalyst prepared in example 6, 100g of alpha-pinene and 10mL of 1, 3-propanediol were placed in a reaction kettle, vacuum was applied for 10 minutes at a gauge pressure of 0.09MPa, nitrogen gas was used for substitution three times at 0.5MPa, hydrogen gas was used for substitution six times at 0.5MPa, and the reaction kettle was checked for leaks and was confirmed to be sealed well. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, and stirring for reacting for 8 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 95.3%, and the yield is 95.3%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 98.5%, the selectivity of cis-pinane was 95.2%, and the yield was 93.8% in the same reaction time.
Example 10 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
The catalytic hydrogenation of alpha-pinene was the same as in example 8, except that the hydrogen pressure in the reactor was adjusted to 4.5 MPa. The reaction is stirred for 5 hours, the conversion rate of the alpha-pinene is 100 percent, the selectivity of the cis-pinane is 95.5 percent, and the yield is 95.5 percent.
Example 11 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
The catalytic hydrogenation of alpha-pinene was the same as in example 8, except that the hydrogen pressure in the reactor was adjusted to 1.5 MPa. The reaction is stirred for 11 hours, the conversion rate of the alpha-pinene is 100 percent, the selectivity of the cis-pinane is 95.1 percent, and the yield is 95.1 percent.
Example 12 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
The catalytic hydrogenation reaction of alpha-pinene is the same as that in example 8, except that the reaction temperature in the reaction kettle is controlled to be 30 ℃. The stirring reaction is carried out for 26 hours, the conversion rate of the alpha-pinene is 96 percent, the selectivity of the cis-pinane is 95.0 percent, and the yield is 91.2 percent.
Example 13 preparation of cis-pinane by hydrogenation of alpha-pinene with skeletal nickel catalyst
The catalytic hydrogenation reaction of alpha-pinene is the same as that in example 8, except that the reaction temperature in the reaction kettle is controlled to 70 ℃. The reaction is stirred for 5 hours, the conversion rate of the alpha-pinene is 100 percent, the selectivity of the cis-pinane is 94.7 percent, and the yield is 94.7 percent.
Example 14 preparation of cis-pinane by hydrogenation of alpha-pinene using modified Raney nickel catalyst
1. Preparation of modified Raney nickel catalyst
Dispersing 11g of 60-80 mesh Raney nickel in 100g of water, adding a formalin solution with the weight of 5% of that of the Raney nickel, stirring for 2 hours at 25 ℃ under the protection of nitrogen, filtering, washing with deionized water for three times to obtain the modified Raney nickel catalyst, and finally storing in the water at 25 ℃.
2. Catalytic hydrogenation reaction of alpha-pinene
The modified Raney nickel catalyst 1.0g and 100g alpha-pinene prepared in the example were placed in a reaction vessel, vacuum-pumping was carried out for 10 minutes under a gauge pressure of 0.05MPa, nitrogen gas was used for three times under 0.5MPa, hydrogen gas was used for three times under 0.5MPa, leak detection was carried out, and it was confirmed that the reaction vessel was well sealed. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 2.5MPa, heating to 60 ℃, adjusting the stirring speed to be 600r/min, and stirring for reacting for 8 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 97.4%, and the yield is 97.4%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 99.7%, the selectivity of cis-pinene was 96.9%, and the yield was 96.6% in the same reaction time.
Example 15 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The preparation of the modified Raney nickel catalyst is the same as that of the modified Raney nickel catalyst in example 14, and the only difference is that the Raney nickel used is 20-40 meshes. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 14, the stirring reaction is carried out for 11 hours, the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 96.2%, and the yield is 96.2%.
Example 16 preparation of cis-pinane by hydrogenation of alpha-pinene using modified Raney nickel catalyst
The modified raney nickel catalyst was prepared the same as example 14, except that raney nickel was used for 100 mesh. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 14, and the stirring reaction is carried out for 6 hours, so that the conversion rate of alpha-pinene is 100%, the selectivity of cis-pinane is 97.8%, and the yield is 97.8%.
Example 17 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The preparation of the modified Raney nickel catalyst is the same as that of the example 14, the only difference is that 28g of 60-80 mesh Raney nickel is dispersed in 100g of water, and other operation steps and reaction conditions of the modification are the same as those of the example 14. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 14, the stirring reaction is carried out for 8 hours, the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 97.6%, and the yield is 97.6%.
Example 18 preparation of cis-pinane by hydrogenation of alpha-pinene using modified Raney nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 14, except that stirring was carried out at 50 ℃ for 2 hours under nitrogen, and the other operating steps and reaction conditions for the modification were the same as in example 14. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 14, the stirring reaction is carried out for 8 hours, the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 97.4%, and the yield is 97.4%.
Example 19 preparation of cis-pinane by hydrogenation of alpha-pinene using modified Raney nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 14, except that stirring was carried out at 75 ℃ for 2 hours under nitrogen, and the other operating steps and reaction conditions for the modification were the same as in example 14. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 14, the stirring reaction is carried out for 8 hours, the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 97.2%, and the yield is 97.2%.
Example 20 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 14. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 14, except that the reaction temperature in the reaction kettle is controlled to 35 ℃. The reaction was stirred for 16 hours, the conversion of alpha-pinene was 100%, the selectivity of cis-pinane was 97.6%, and the yield was 97.6%.
Example 21 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 14. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 14, except that the reaction temperature in the reaction kettle is controlled to 90 ℃. The reaction is stirred for 6 hours, the conversion rate of the alpha-pinene is 100 percent, the selectivity of the cis-pinane is 97.1 percent, and the yield is 97.1 percent.
Example 22 preparation of cis-pinane by hydrogenation of alpha-pinene using modified Raney nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 14. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene were the same as those in example 14, except that the reaction pressure in the reaction vessel was adjusted to 1.5 MPa. The reaction was stirred for 20 hours, the conversion of alpha-pinene was 100%, the selectivity of cis-pinane was 96.7%, and the yield was 96.7%.
Example 23 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 14. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene were the same as those in example 14, except that the reaction pressure in the reaction vessel was adjusted to 3.0 MPa. The reaction was stirred for 6 hours, the conversion of alpha-pinene was 100%, the selectivity of cis-pinane was 97.6%, and the yield was 97.6%.
Example 24 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 14. The experimental operation and reaction conditions of the alpha-pinene catalytic hydrogenation reaction are the same as those in example 14, except that the reaction pressure in the hydrogenation reaction kettle is adjusted to 4.0 MPa. The stirring reaction is carried out for 5.5 hours, the conversion rate of the alpha-pinene is 100 percent, the selectivity of the cis-pinane is 97.8 percent, and the yield is 97.8 percent.
Example 25 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
1. Preparation of modified Raney nickel catalyst
Dispersing 28g of 60-80 mesh Raney nickel in 100g of methanol, adding a formalin solution with the weight of 10% of that of the Raney nickel, stirring for 1 hour at 50 ℃ under the protection of inert gas, filtering, washing with deionized water for three times to obtain the modified Raney nickel catalyst, and finally storing in water with the temperature of 25 ℃.
2. Catalytic hydrogenation reaction of alpha-pinene
2.5g of the prepared modified Raney nickel catalyst and 100g of alpha-pinene are placed in a reaction kettle, vacuumizing is carried out for 10 minutes under the gauge pressure of 0.03MPa, nitrogen is used for replacing for three times under the pressure of 0.3MPa, hydrogen is used for replacing for three times under the pressure of 0.3MPa, and leakage detection is carried out to confirm that the reaction kettle is well sealed. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 3.0MPa, heating to 70 ℃, adjusting the stirring speed to be 750r/min, and stirring for 5 hours to react, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 97.8%, and the yield is 97.8%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 99%, the selectivity of cis-pinene was 97.5%, and the yield was 96.5% in the same reaction time.
Example 26 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 25, except that raney nickel was dispersed in ethanol and the other operating steps and reaction conditions for the modification were the same as in example 25. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 22, and the stirring reaction is carried out for 5 hours, so that the conversion rate of alpha-pinene is 100%, the selectivity of cis-pinane is 97.8%, and the yield is 97.8%.
Example 27 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 25, except that raney nickel was dispersed in 1, 3-propanediol and the other operating steps and reaction conditions for the modification were the same as in example 25. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 25, and the stirring reaction is carried out for 5 hours, so that the conversion rate of alpha-pinene is 100%, the selectivity of cis-pinane is 97.8%, and the yield is 97.8%.
Example 28 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 25. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 25, except that 5.0g and 100g of the modified raney nickel catalyst are put in a reaction kettle, other operation steps and reaction conditions are the same as those in example 25, the stirring reaction is carried out for 5 hours, the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 97.9%, and the yield is 97.9%.
Example 29 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
The modified raney nickel catalyst was prepared the same as in example 25 except that raney nickel was dispersed in a mixed solution of water and ethanol (wherein the mass fractions of water and ethanol were each 50%), and the other operating steps and reaction conditions for the modification were the same as in example 25. The experimental operation and reaction conditions of the catalytic hydrogenation reaction of alpha-pinene are the same as those in example 25, and the stirring reaction is carried out for 5 hours, so that the conversion rate of alpha-pinene is 100%, the selectivity of cis-pinane is 97.8%, and the yield is 97.8%.
Example 30 preparation of cis-pinane by hydrogenation of alpha-pinene Using modified Raney Nickel catalyst
2.5g of the Raney nickel catalyst prepared in EXAMPLE 25, 100g of α -pinene and 20mL of methanol were placed in a reaction vessel, and vacuum was applied at a gauge pressure of 0.03MPa for 10 minutes, and nitrogen gas was used for three times at 0.3MPa, and hydrogen gas was used for three times at 0.3MPa, and the vessel was tested for leaks, and it was confirmed that the vessel was sealed well. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 3.0MPa, heating to 70 ℃, adjusting the stirring speed to be 750r/min, and stirring for reaction for 7 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 97.3%, and the yield is 97.3%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 98.2%, the selectivity of cis-pinene was 96.8%, and the yield was 95.1% in the same reaction time.
Example 31 preparation of cis-pinane by hydrogenation of alpha-pinene using modified Raney nickel catalyst
2.5g of the Raney nickel catalyst prepared in EXAMPLE 25, 100g of α -pinene and 20mL of 1-propanol were placed in a reaction vessel, and vacuum was applied at a gauge pressure of 0.03MPa for 10 minutes, and the reaction vessel was replaced with nitrogen gas three times at a pressure of 0.3MPa and then with hydrogen gas three times at a pressure of 0.3MPa, and the sealing was checked to confirm that the reaction vessel was sealed properly. And opening a hydrogen gas inlet valve, adjusting the pressure in the kettle to be 3.0MPa, heating to 70 ℃, adjusting the stirring speed to be 750r/min, and stirring for reaction for 7 hours, wherein the conversion rate of the alpha-pinene is 100%, the selectivity of the cis-pinane is 97.4%, and the yield is 97.4%.
After each reaction, the catalyst was recovered, and the catalyst hydrogenation reaction of α -pinene in this example was repeated with the recovered catalyst, and it was found that after the catalyst was reused 10 times, under the same experiment and operation conditions in this example, the conversion of α -pinene was 98.3%, the selectivity of cis-pinene was 96.7%, and the yield was 95.1% in the same reaction time.
Comparative example 1 preparation of cis-pinane by hydrogenation of alpha-pinene with Raney nickel catalyst
The experimental operating procedure and reaction conditions for the hydrogenation of alpha-pinene were the same as those in example 14, except that the catalyst used raney nickel before modification in example 14. After the reaction, sampling analysis shows that the conversion rate of alpha-pinene is 100%, the selectivity of cis-pinane is 89.0% and the yield is 87.5%.
It should be noted that, although the above embodiments have been described herein, the scope of the present invention is not limited thereby, and the technical parameters and raw material components which are not described in detail can still obtain the same or similar technical effects as the above embodiments when they are changed within the range of the parameters listed in the present invention, and still fall within the scope of the present invention. Therefore, based on the innovative concepts of the present invention, the technical solutions of the present invention can be directly or indirectly applied to other related technical fields by making changes and modifications to the embodiments described herein or by using equivalent structures or equivalent processes performed in the present specification, and are included in the scope of the present invention.

Claims (15)

1. A catalyst for preparing cis-pinane by hydrogenating alpha-pinene is characterized in that the catalyst is a skeletal nickel catalyst, and nickel, aluminum and molybdenum elements are used as raw materials;
in the raw materials, molybdenum exists in a form of doped elements, the weight ratio of molybdenum to nickel is 1-12%, and the weight ratio of molybdenum to aluminum is 1-15%.
2. The catalyst according to claim 1, wherein the weight ratio of molybdenum to nickel in the raw material is 1 to 7%, and the weight ratio of molybdenum to aluminum is 1 to 6%.
3. A process for preparing the catalyst of claim 1 or 2, comprising the steps of:
step (1): slowly adding nickel-aluminum alloy particles or fine powder containing a doping element molybdenum into an inorganic alkali liquor, and controlling the temperature of the inorganic alkali liquor within the range of 10-80 ℃ to react for 0.5-3 hours after the addition is finished;
step (2): raising the temperature of the inorganic alkali liquor in the step (1) to 80-105 ℃, and reacting for 1-12 hours in a heat preservation manner to obtain a reaction mixture;
and (3): and (3) filtering out a solid in the reaction mixture in the step (2), washing the solid to be neutral by using water, and storing the solid in alcohol at the temperature of-30 ℃.
4. The method of claim 3, wherein the inorganic alkali solution is NaOH aqueous solution or KOH aqueous solution; the mass percentage concentration of the NaOH aqueous solution or the KOH aqueous solution is 10-50%.
5. A method for preparing cis-pinane by catalyzing hydrogenation of alpha-pinene is characterized by comprising the following steps:
the use of the catalyst of claim 1 or 2 for the preparation of cis-pinane by hydrogenation of α -pinene.
6. The method according to claim 5, characterized in that it comprises the steps of:
step (1): placing alpha-pinene and the skeletal nickel catalyst into a reaction kettle;
step (2): vacuumizing for 10 minutes under the gauge pressure of 0.01-0.09 MPa, replacing for 3-4 times under the pressure of 0.1-0.5 MPa by using nitrogen, replacing for 3-6 times under the pressure of 0.1-0.5 MPa by using hydrogen, detecting leakage, and confirming that the reaction kettle is well sealed;
and (3): and opening a hydrogen gas inlet valve, adjusting the pressure in the reaction kettle to be 0.2-6 MPa, raising the temperature in the reaction kettle to 30-70 ℃, adjusting the stirring speed to be 500-1000 r/min, and reacting for 2-8 hours.
7. The method of claim 6, wherein in step (1), the skeletal nickel catalyst is used in an amount of 0.5-10% by weight of the α -pinene.
8. The method according to claim 6, wherein in step (1), the α -pinene is present in a solvent-free form.
9. The method according to claim 6, wherein in step (1), the α -pinene is present in the form of a solution dissolved in an organic solvent; the organic solvent is C1-C4 alkanol, and the C1-C4 alkanol is any one of methanol, ethanol, ethylene glycol, 1-propanol, 2-propanol, 1, 2-propanediol, 1, 3-propanediol and 1-butanol.
10. A method for preparing cis-pinane by catalyzing alpha-pinene hydrogenation by using a raney nickel catalyst modified by formalin is characterized by comprising the following steps:
step (1): using formalin to modify a Raney nickel catalyst to obtain a modified Raney nickel catalyst;
step (2): placing alpha-pinene and the modified Raney nickel catalyst into a reaction kettle;
and (3): vacuumizing for 10 minutes under the gauge pressure of 0.01-0.09 MPa, replacing for 3-4 times under the pressure of 0.1-0.5 MPa by using nitrogen, replacing for 3-6 times under the pressure of 0.1-0.5 MPa by using hydrogen, detecting leakage, and confirming that the reaction kettle is well sealed;
and (4): and opening a hydrogen gas inlet valve, adjusting the pressure in the reaction kettle to be 0.1-6 MPa, raising the temperature in the reaction kettle to 35-90 ℃, adjusting the stirring speed to be 500-1000 r/min, and reacting for 4-10 hours.
11. The method of claim 9, wherein in step (2), the modified raney nickel catalyst is used in an amount of 0.7 to 8% by weight of the α -pinene; the alpha-pinene exists in a solvent-free form.
12. The method according to claim 9, wherein in step (2), the α -pinene is present in the form of a solution dissolved in an organic solvent; the organic solvent is C1-C4 alkanol, and the C1-C4 alkanol is any one of methanol, ethanol, ethylene glycol, 1-propanol, 2-propanol, 1, 2-propanediol, 1, 3-propanediol and 1-butanol.
13. The skeletal nickel catalyst is used as the catalyst in the reaction of alpha-pinene hydrogenation to prepare cis-pinane.
14. The use according to claim 13, wherein the skeletal nickel catalyst is prepared from nickel, aluminum and molybdenum elements;
in the raw materials, molybdenum exists in a form of doped elements, the weight ratio of molybdenum to nickel is 1-12%, and the weight ratio of molybdenum to aluminum is 1-15%.
15. The raney nickel catalyst modified by formalin is used as the catalyst in the reaction of alpha-pinene hydrogenation to prepare cis-pinane.
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