CN110330421B - Method for preparing tricyclodecanedicarboxylic acid by taking dicyclopentadiene as raw material - Google Patents

Method for preparing tricyclodecanedicarboxylic acid by taking dicyclopentadiene as raw material Download PDF

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CN110330421B
CN110330421B CN201910789092.9A CN201910789092A CN110330421B CN 110330421 B CN110330421 B CN 110330421B CN 201910789092 A CN201910789092 A CN 201910789092A CN 110330421 B CN110330421 B CN 110330421B
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alumina
alpha
cobalt
manganese
rhodium
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CN110330421A (en
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马昱博
揭芳芳
宋春雨
狄宁
何桅
李小庆
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Chongqing Chemical Industry Vocational College
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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
    • 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
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0269—Phosphorus containing compounds on mineral substrates
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/145—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide with simultaneous oxidation
    • 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
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes

Abstract

The invention belongs to the technical field of preparation of carboxylic acid by carbonylation reaction, and particularly relates to a preparation method of tricyclodecanedicarboxylic acid. The preparation method comprises the following steps: taking dicyclopentadiene as a raw material, taking cobalt rhodium manganese trimetal loaded on phosphine ligand modified alpha-alumina as a catalyst, and controlling the mixed gas pressure of synthesis gas and air to be 4-7MPa, the reaction temperature to be 150-170 ℃, the reaction pressure to be 7-9MPa, and reacting for 3-8h to obtain the catalyst. The method for preparing the tricyclodecanedicarboxylic acid has the advantages that the conversion rate of dicyclopentadiene can reach more than 99 percent, and the selectivity of the tricyclodecanedicarboxylic acid can reach more than 90 percent.

Description

Method for preparing tricyclodecanedicarboxylic acid by taking dicyclopentadiene as raw material
Technical Field
The invention belongs to the technical field of preparation of carboxylic acid by carbonylation reaction, and particularly relates to a method for preparing tricyclodecanedicarboxylic acid by taking dicyclopentadiene as a raw material.
Background
Dicyclopentadiene (DCPD), also known as Dicyclopentadiene, is a by-product of the preparation of acetylene by petroleum cracking and coking with coal. Dicyclopentadiene is a dimer of cyclopentadiene, with a boiling point of 170 deg.C, a melting point of 31.5 deg.C, and a density of 0.9796g/cm3. The dicyclopentadiene has two isomers (shown below) of bridged ring type and hanging ring type in spatial structure, and can be used for preparing the medicine at room temperature
Figure DEST_PATH_IMAGE002
Cyclopentadiene is dimerized to form bridged ring type, and heated to 150 deg.c to dimerize to form ring hanging type, and bridged ring type dicyclopentadiene is used mainly in industry. High-purity dicyclopentadiene is colorless crystals at room temperature, is a pale yellow oily liquid when containing impurities, has pungent camphor flavor, is insoluble in water, and is soluble in organic solvents such as alcohols and ethers ("new progress in dicyclopentadiene research", wangwei et al, chemical and adhesive, vol.29, No. 2, p.117, left column, lines 1-9, published 2007, 12-31).
Because dicyclopentadiene (DCPD) can be converted into Cyclopentadiene (CPD) at a certain temperature, the application route of dicyclopentadiene is greatly widened. From basic organic chemical raw materials to novel polymer materials, dicyclopentadiene has important and obtained applications, such as being used in the fields of medicines, dyes, catalysts, conductors, semiconductors, special magnetic materials, coatings, catalysts, heat-resistant materials, perfumes, rubbers, plastics, paper making, adhesives, inks, machines, electronic device housings, building materials, various tool parts and the like ("production and application of dicyclopentadiene", chapter equi, etc., fine and specialty chemicals, volume 12, 11 th, page 8, right-hand column, 1 st to 4 th lines at the right-hand column of the 8 th, 3 rd lines at the left-hand column of the 9 th, 4 th to 5 th lines at the left-hand column of the 9 th, 1 st to 3 th lines at the left-hand column of the 10 th, 1 st to 3 th lines at the right-hand column of the 10 th, 1 st to 1 st lines at the right-hand column of the 12 th, 1 st to 8 th lines at the right-hand column of the 12 th and 4 th to 6 th lines at the left-hand column of the 13 th, 6/2004).
At present, the modes of high additivity of dicyclopentadiene mainly include the following two modes: (1) directly hydrogenating and isomerizing to produce high-density fuel; (2) the carbonylation reaction produces tricyclodecanedicarbaldehyde, which is further hydrogenated to produce tricyclodecanedimethanol, or the oxidation produces tricyclodecanedicarboxylic acid ("dicyclopentadiene continuously polymerizes to produce high density fuel", Jiangkai, university of Tianjin, university of Master academic thesis, 2007, page 6, paragraphs 2, lines 1 to 3, published date 2009, 1 month 14; "ferromagnetic oxide supported dicyclopentadiene hydroformylation on rhodium-based catalyst", Mayibo et al, fourteenth national youth conference on catalysis, proceedings 2013, page 1, paragraphs 1, lines 2, published date 2014, 9 months 30).
Both of them can produce high-performance polyester which is highly flat, non-discoloring, heat-resistant and corrosion-resistant, based on the rigid ring structures of tricyclodecanedimethanol and tricyclodecanedicarboxylic acid. Polyesters based on tricyclodecanedimethanol have been reported, the best known of which is the production technology of the German winning company. Polyesters based on tricyclodecane dicarboxylic acid have not been reported, mainly because the technology for producing tricyclodecane dicarboxylic acid is still in the beginning.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing tricyclodecanedicarboxylic acid using dicyclopentadiene as a raw material.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a process for the preparation of tricyclodecanedicarboxylic acid comprising the steps of:
taking dicyclopentadiene as a raw material, taking cobalt rhodium manganese trimetal loaded on phosphine ligand modified alpha-alumina as a catalyst, and controlling the mixed gas pressure of synthesis gas and air to be 4-7MPa, the reaction temperature to be 150-170 ℃, the reaction pressure to be 7-9MPa, and reacting for 3-8h to obtain the catalyst.
The inventor unexpectedly finds that the method comprises the following steps: taking dicyclopentadiene as a raw material, taking cobalt, rhodium and manganese trimetal loaded on phosphine ligand modified alpha-alumina as a catalyst, and controlling the mixed gas pressure of synthesis gas and air to be 4-7MPa, the reaction temperature to be 150-170 ℃, the reaction pressure to be 7-9MPa and the reaction time to be 3-8h in the presence of an organic solvent; the method for preparing the tricyclodecanedicarboxylic acid has the advantages that the conversion rate of dicyclopentadiene can reach more than 99 percent, and the selectivity of the tricyclodecanedicarboxylic acid can reach more than 90 percent.
Further, the phosphine ligand comprises triphenylphosphine, tributylphosphine, triphenylphosphine oxide or triphenylphosphine sodium tri-m-sulfonate.
Further, the mass ratio of the phosphine ligand to the cobalt, rhodium and manganese trimetal loaded on the alpha-alumina is 1:3-1: 6.
Further, the dosage of the cobalt rhodium manganese trimetallic catalyst loaded on the phosphine ligand modified alpha-alumina is 3-5% of the mass of the dicyclopentadiene.
Further, the organic solvent is toluene, n-hexane or tetrahydrofuran.
Further, the organic solvent is used in such an amount that the final concentration of dicyclopentadiene is 0.1-0.3 g/mL.
Further, the catalyst is prepared by the following steps: preparing cobalt rhodium manganese oxide supported by alpha-alumina, then carrying out hydrogenation reduction on the cobalt rhodium manganese oxide supported by the alpha-alumina to obtain cobalt rhodium manganese trimetal supported by the alpha-alumina, then carrying out phosphine ligand modification on the cobalt rhodium manganese trimetal supported by the alpha-alumina, wherein the phosphine ligand modification specifically comprises the steps of reacting the cobalt rhodium manganese trimetal supported by the alpha-alumina and a phosphine ligand in tetrahydrofuran for 0.5-2h, and then removing the tetrahydrofuran.
Further, the mass ratio of the phosphine ligand to the cobalt, rhodium and manganese trimetal loaded on the alpha-alumina is 1:3-1: 6.
Further, the solvent is removed by vacuum pumping at 20-45 ℃.
Further, the preparation of the alpha-alumina supported cobalt rhodium manganese oxide comprises the following steps: dissolving aluminum isopropoxide in ethanol, stirring and heating to 60-80 ℃ to obtain an ethanol solution of aluminum isopropoxide; dissolving manganese nitrate, cobalt chloride and rhodium trichloride in water, then adding the solution into an ethanol solution of aluminum isopropoxide, then adding a nitric acid solution, reacting at 60-80 ℃ for 24-72h, and roasting at 400-600 ℃ for 3-6 h.
Further, the volume ratio of the isopropanol to the ethanol is 20:14-28: 14.
Further, the hydrogenation reduction comprises the following steps: firstly reducing for 2-4h at the temperature of 400-600 ℃ in hydrogen, cooling to room temperature, then roasting for 3-6h at the temperature of 400-600 ℃ in air, and then reducing for 2-4h at the temperature of 600 ℃ in hydrogen.
Further, the preparation method of the tricyclodecanedicarboxylic acid comprises the following steps:
A. dissolving aluminum isopropoxide in ethanol, stirring and heating to 60-80 ℃ to obtain an ethanol solution of aluminum isopropoxide; dissolving manganese nitrate, cobalt chloride and rhodium trichloride in water, then adding the solution into an ethanol solution of aluminum isopropoxide, then adding a nitric acid solution, reacting at 60-80 ℃ for 24-72h, and roasting at 400-600 ℃ for 3-6h to prepare cobalt-rhodium-manganese oxide supported by alpha-alumina;
B. firstly reducing cobalt rhodium manganese oxide supported by alpha-alumina for 2-4h at 400-600 ℃, cooling to room temperature, then roasting in air at 400-600 ℃ for 3-6h, then reducing for 2-4h at 400-600 ℃ in hydrogen to obtain cobalt rhodium manganese trimetal supported by alpha-alumina, then carrying out phosphine ligand modification on the cobalt rhodium manganese trimetal supported by alpha-alumina, wherein the phosphine ligand modification specifically comprises the steps of reacting the cobalt rhodium manganese trimetal supported by alpha-alumina and a phosphine ligand in tetrahydrofuran for 0.5-2h, and then removing the tetrahydrofuran by vacuumizing at 20-45 ℃; the phosphine ligand comprises triphenylphosphine, tributylphosphine, triphenylphosphine oxide or triphenylphosphine sodium tri-m-sulfonate, and the mass ratio of the phosphine ligand to the cobalt rhodium manganese trimetal loaded on the alpha-alumina is 1:3-1: 6;
C. sequentially introducing dicyclopentadiene, a cobalt-rhodium-manganese trimetallic catalyst loaded on alpha-alumina modified by a phosphine ligand and an organic solvent into a reaction kettle, sealing, controlling the pressure of a mixed gas of synthesis gas and air to be 4-7MPa, the reaction temperature to be 150-170 ℃, the reaction pressure to be 7-9MPa, and reacting for 3-8 hours to obtain the catalyst; the dosage of the cobalt rhodium manganese trimetallic catalyst supported by the phosphine ligand modified alpha-alumina is 3 to 5 percent of the mass of the dicyclopentadiene; the organic solvent is toluene, n-hexane or tetrahydrofuran, and the dosage of the organic solvent is that the final concentration of dicyclopentadiene is 0.1-0.3 g/mL.
The invention also aims to protect a catalyst for catalyzing dicyclopentadiene to synthesize tricyclodecane dicarboxylic acid, which comprises cobalt rhodium manganese trimetal supported on phosphine ligand modified alpha-alumina.
The inventor unexpectedly finds that when the catalyst containing cobalt, rhodium and manganese trimetallic supported on phosphine ligand modified alpha-alumina is used for catalyzing dicyclopentadiene to synthesize tricyclodecanedicarboxylic acid, the conversion rate of dicyclopentadiene can reach more than 99%, and the selectivity of tricyclodecanedicarboxylic acid can reach more than 90%.
Further, the phosphine ligand comprises triphenylphosphine, tributylphosphine, triphenylphosphine oxide or triphenylphosphine sodium tri-m-sulfonate.
Further, the mass ratio of the phosphine ligand to the cobalt, rhodium and manganese trimetal loaded on the alpha-alumina is 1:3-1: 6.
Further, the dosage of the cobalt rhodium manganese trimetallic catalyst loaded on the phosphine ligand modified alpha-alumina is 3-5% of the mass of the dicyclopentadiene.
The invention also aims to protect the preparation method of the catalyst, comprising the following steps:
preparing cobalt rhodium manganese oxide supported by alpha-alumina, then carrying out hydrogenation reduction on the cobalt rhodium manganese oxide supported by the alpha-alumina to obtain cobalt rhodium manganese trimetal supported by the alpha-alumina, then carrying out phosphine ligand modification on the cobalt rhodium manganese trimetal supported by the alpha-alumina, wherein the phosphine ligand modification specifically comprises the steps of reacting the cobalt rhodium manganese trimetal supported by the alpha-alumina and a phosphine ligand in tetrahydrofuran for 0.5-2h, and then removing the tetrahydrofuran.
The inventor unexpectedly finds that the catalyst comprising cobalt rhodium manganese trimetal supported by phosphine ligand modified alpha-alumina is used for preparing tricyclodecane dicarboxylic acid in a catalytic mode, and the catalytic activity and the reaction selectivity are high.
Further, the phosphine ligand comprises triphenylphosphine, tributylphosphine, triphenylphosphine oxide or triphenylphosphine sodium tri-m-sulfonate.
Further, the mass ratio of the phosphine ligand to the cobalt, rhodium and manganese trimetal loaded on the alpha-alumina is 1:3-1: 6.
The invention also aims to protect the preparation method of the catalyst, comprising the following steps:
preparing cobalt rhodium manganese oxide supported by alpha-alumina, then carrying out hydrogenation reduction on the cobalt rhodium manganese oxide supported by the alpha-alumina to obtain cobalt rhodium manganese trimetal supported by the alpha-alumina, then carrying out phosphine ligand modification on the cobalt rhodium manganese trimetal supported by the alpha-alumina, wherein the phosphine ligand modification specifically comprises the steps of reacting the cobalt rhodium manganese trimetal supported by the alpha-alumina and a phosphine ligand in tetrahydrofuran for 0.5-2h, and then removing the tetrahydrofuran.
Further, the solvent is removed by vacuum pumping at 20-45 ℃.
Further, the preparation of the alpha-alumina supported cobalt rhodium manganese oxide comprises the following steps: dissolving aluminum isopropoxide in ethanol, stirring and heating to 60-80 ℃ to obtain an ethanol solution of aluminum isopropoxide; dissolving manganese nitrate, cobalt chloride and rhodium trichloride in water, then adding the solution into an ethanol solution of aluminum isopropoxide, then adding a nitric acid solution, reacting at 60-80 ℃ for 24-72h, and roasting at 400-600 ℃ for 3-6 h.
Further, the volume ratio of the isopropanol to the ethanol is 20:14-28: 14.
Further, the manganese nitrate, the cobalt chloride and the rhodium trichloride are dissolved in water so as to make the final concentration of the manganese nitrate be 0.3g/mL, 0.03g/mL and 0.03 g/mL.
Further, the volume ratio of the nitric acid solution to the ethanol solution of aluminum isopropoxide is 3:17-5: 17.
Further, the hydrogenation reduction comprises the following steps: firstly reducing for 2-4h at the temperature of 400-600 ℃ in hydrogen, cooling to room temperature, then roasting for 3-6h at the temperature of 400-600 ℃ in air, and then reducing for 2-4h at the temperature of 600 ℃ in hydrogen.
Further, the preparation method of the catalyst comprises the following steps:
dissolving aluminum isopropoxide in ethanol according to the volume ratio of 20:14-28:14 to ethanol, stirring and heating to 60-80 ℃ to obtain an ethanol solution of aluminum isopropoxide; dissolving manganese nitrate, cobalt chloride and rhodium trichloride in water to enable the final concentrations of the manganese nitrate to be 0.3g/mL, 0.03g/mL and 0.03g/mL, then adding the manganese nitrate into an ethanol solution of aluminum isopropoxide, then adding a nitric acid solution, reacting for 24-72h at 60-80 ℃, and then roasting for 3-6h at 400-600 ℃ to prepare the alpha-alumina supported cobalt rhodium manganese oxide; the volume ratio of the nitric acid solution to the ethanol solution of aluminum isopropoxide is 3:17-5: 17;
then reducing the cobalt rhodium manganese oxide supported by the alpha-alumina for 2-4h in hydrogen at 400-600 ℃, cooling to room temperature, then roasting in air at 400-600 ℃ for 3-6h, and then reducing in hydrogen at 400-600 ℃ for 2-4h to obtain cobalt rhodium manganese trimetal supported by the alpha-alumina;
then the cobalt rhodium manganese trimetal loaded on the alpha-alumina and the phosphine ligand react in tetrahydrofuran for 0.5 to 2 hours, and the tetrahydrofuran is removed by vacuum pumping at the temperature of between 20 and 45 ℃; the phosphine ligand comprises triphenylphosphine, tributylphosphine, triphenylphosphine oxide or triphenylphosphine sodium tri-m-sulfonate, and the mass ratio of the phosphine ligand to the cobalt rhodium manganese trimetal loaded on the alpha-alumina is 1:3-1: 6.
The invention has the beneficial effects that:
the method for preparing the tricyclodecanedicarboxylic acid has the advantages that the conversion rate of dicyclopentadiene can reach more than 99 percent, and the selectivity of the tricyclodecanedicarboxylic acid can reach more than 90 percent.
The method has the advantages of relatively mild reaction conditions and relatively short reaction time.
The method of the invention simplifies the preparation process of the tricyclodecanedicarboxylic acid.
The catalyst and the reaction system of the method are convenient to separate, can be repeatedly used, and are convenient to amplify and apply industrially.
The catalyst of the invention has relatively low price and the preparation method is relatively simple.
The preparation method has the advantages of relatively mild conditions, relatively short reaction time and simple process.
Detailed Description
The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
Example 1
The preparation method of the phosphine ligand modified alpha-alumina supported cobalt rhodium manganese trimetal comprises the following specific steps:
a: dissolving 20ml of aluminum isopropoxide in 14ml of ethanol, and heating to 60 ℃ under the condition of stirring to obtain an ethanol solution of the aluminum isopropoxide;
b: dissolving 3g of manganese nitrate, 0.3g of cobalt chloride and 0.3g of rhodium trichloride in 10ml of distilled water, adding the solution into the ethanol solution of aluminum isopropoxide prepared in the step A, then adding a mixed solution of 5ml of concentrated nitric acid and 5ml of water, and aging at 60 ℃ for 24 hours; then roasting for 6 hours at 400 ℃ in a muffle furnace under the air atmosphere to obtain cobalt rhodium manganese oxide supported by alpha-alumina;
c: b, reducing the alpha-alumina-supported cobalt rhodium manganese oxide prepared in the step B in hydrogen at 400 ℃ for 4h, cooling to room temperature, roasting in air at 400 ℃ for 6h, and finally reducing in hydrogen at 400 ℃ for 4h to obtain 6g of alpha-alumina-supported cobalt rhodium manganese trimetal;
d: 6g of cobalt rhodium manganese trimetal loaded on alpha-alumina and 1g of triphenylphosphine are added into tetrahydrofuran, stirred for 0.5h at room temperature, and then the tetrahydrofuran is removed by vacuumizing at the temperature of 20 ℃ to obtain the cobalt rhodium manganese trimetal loaded on the triphenylphosphine modified alpha-alumina.
Example 2
The preparation of tricyclodecanedicarboxylic acid comprises the following specific steps:
5g of dicyclopentadiene (DCPD), 0.15g of cobalt rhodium manganese trimetal loaded on triphenylphosphine modified alpha-alumina prepared in example 1 and 20ml of tetrahydrofuran are sequentially introduced into a 200ml high-pressure reaction kettle, the reaction kettle is sealed, air and synthesis gas (the volume ratio of 1/1) are filled to 5 MPa, the reaction temperature is 160 ℃, the reaction pressure is 8 MPa, and the tricyclodecanedicarboxylic acid can be obtained after the reaction is carried out for 6 hours.
Example 3
The preparation method of the phosphine ligand modified alpha-alumina supported cobalt rhodium manganese trimetal comprises the following specific steps:
a: dissolving 28ml of aluminum isopropoxide in 14ml of ethanol, and heating to 80 ℃ under the condition of stirring to obtain an ethanol solution of the aluminum isopropoxide;
b: dissolving 3g of manganese nitrate, 0.3g of cobalt chloride and 0.3g of rhodium trichloride in 10ml of distilled water, adding the obtained solution into the ethanol solution of aluminum isopropoxide prepared in the step A, adding a mixed solution of 5ml of concentrated nitric acid and 5ml of water, aging at 80 ℃ for 72h, and roasting at 600 ℃ for 3h in a muffle furnace under the air atmosphere to obtain cobalt-rhodium-manganese oxide supported by alpha-alumina;
c: reducing the alpha-alumina-supported cobalt rhodium manganese oxide prepared in the step B in hydrogen at 600 ℃ for 2h, cooling to room temperature, roasting in air at 600 ℃ for 3h, and finally reducing in hydrogen at 600 ℃ for 2h to obtain alpha-alumina silicon-supported cobalt rhodium manganese trimetal;
d: 6g of cobalt rhodium manganese trimetal supported by alpha-alumina and 1g of tributylphosphine are added into tetrahydrofuran, stirred for 2 hours at room temperature, and then the tetrahydrofuran is removed by vacuumizing at the temperature of 45 ℃ to obtain the cobalt rhodium manganese trimetal supported by the tributylphosphine modified alpha-alumina.
Example 4
The preparation of tricyclodecanedicarboxylic acid comprises the following specific steps:
2g of dicyclopentadiene (DCPD), 0.25 g of cobalt rhodium manganese trimetal loaded on tributylphosphine modified alpha-alumina prepared in example 3 and 20ml of organic solvent n-hexane are sequentially introduced into a 200ml high-pressure reaction kettle, the reaction kettle is sealed, air and synthesis gas (the volume ratio of 1/4) are filled to 6 MPa, the reaction temperature is 150 ℃, the reaction pressure is 8 MPa, and the tricyclodecanedicarboxylic acid is obtained after the reaction is carried out for 3 hours.
Example 5
The preparation method of the phosphine ligand modified alpha-alumina supported cobalt rhodium manganese trimetal comprises the following specific steps:
a: dissolving 20ml of aluminum isopropoxide in 14ml of ethanol, and heating to 70 ℃ under the condition of stirring to obtain an ethanol solution of the aluminum isopropoxide;
b: dissolving 3g of manganese nitrate, 0.3g of cobalt chloride and 0.3g of rhodium trichloride in 10ml of distilled water, adding the obtained solution into the ethanol solution of aluminum isopropoxide prepared in the step A, adding a mixed solution of 3ml of concentrated nitric acid and 5ml of water, aging at 70 ℃ for 48h, and roasting at 500 ℃ for 4h in a muffle furnace under the air atmosphere to obtain cobalt-rhodium-manganese oxide supported by alpha-alumina;
c: reducing the alpha-alumina-supported cobalt rhodium manganese oxide prepared in the step B in hydrogen for 3h at 500 ℃, cooling to room temperature, roasting in air at 500 ℃ for 4h, and finally reducing in hydrogen for 3h at 500 ℃ to obtain alpha-alumina-supported cobalt rhodium manganese and gold;
d: 6g of cobalt rhodium manganese and gold supported by alpha-alumina and triphenylphosphine oxide are added into tetrahydrofuran, stirred for 1h at room temperature, and then the tetrahydrofuran is removed by vacuumizing at the temperature of 35 ℃ to obtain cobalt rhodium manganese trimetal supported by the triphenylphosphine oxide modified alpha-alumina.
Example 6
The preparation of tricyclodecanedicarboxylic acid comprises the following specific steps:
6g of dicyclopentadiene (DCPD), 0.2g of cobalt rhodium manganese trimetal loaded on triphenylphosphine oxide modified alpha-alumina prepared in example 5 and 20ml of organic solvent toluene are sequentially introduced into a 200ml high-pressure reaction kettle, the reaction kettle is sealed, air and synthesis gas (the volume ratio of 1/3) are filled to 4 MPa, the reaction temperature is 160 ℃, the reaction pressure is 7MPa, and the tricyclodecanedicarboxylic acid is obtained after the reaction is carried out for 8 hours.
Example 7
Preparing an alpha-alumina supported cobalt rhodium manganese trimetal catalyst:
a: dissolving 20ml of aluminum isopropoxide in 14ml of ethanol, and heating to 60 ℃ under the condition of stirring to obtain an ethanol solution of the aluminum isopropoxide;
b: dissolving 3g of manganese nitrate, 0.3g of cobalt chloride and 0.3g of rhodium trichloride in 10ml of distilled water, adding the obtained solution into the ethanol solution of aluminum isopropoxide prepared in the step A, adding a mixed solution of 5ml of concentrated nitric acid and 5ml of water, aging at 60 ℃ for 24h, and roasting at 400 ℃ for 6h in a muffle furnace under the air atmosphere to obtain cobalt-rhodium-manganese oxide supported by alpha-alumina;
c: reducing the alpha-alumina-supported cobalt rhodium manganese oxide prepared in the step B in hydrogen at 400 ℃ for 4h, cooling to room temperature, roasting in air at 400 ℃ for 6h, and finally reducing in hydrogen at 400 ℃ for 4h to obtain alpha-alumina-supported cobalt rhodium manganese trimetal;
d: adding cobalt rhodium manganese trimetal loaded on 6 alpha-alumina and 1g of triphenylphosphine sodium tri-m-sulfonate into tetrahydrofuran, stirring for 0.5h at room temperature, and then vacuumizing at 35 ℃ to remove tetrahydrofuran to obtain the cobalt rhodium manganese trimetal loaded on the alpha-alumina modified by the triphenylphosphine sodium tri-m-sulfonate;
example 8
The preparation of tricyclodecanedicarboxylic acid comprises the following specific steps:
5g of dicyclopentadiene (DCPD), 0.2g of cobalt rhodium manganese trimetal loaded on the phenylphosphine sodium trimetaphosphate modified alpha-alumina prepared in example 7 and 20ml of organic solvent ethanol are sequentially introduced into a 200ml high-pressure reaction kettle, the reaction kettle is sealed, air and synthesis gas (the volume ratio of 1/2) are filled to 4 MPa, the reaction temperature is 150 ℃, the reaction pressure is 9MPa, and the tricyclodecanedicarboxylic acid is obtained after the reaction for 3 hours.
Performance detection
The conversion of dicyclopentadiene (DCPD) and the selectivity of tricyclodecanedicarboxylic acid were measured in examples 2, 4, 6 and 8, and the results are shown in table 1;
the quantitative detection method of dicyclopentadiene comprises the following steps: determining by gas chromatography, wherein the detector is hydrogen flame detector, the chromatography conditions are that the sample inlet is 250 deg.C, the detector is 250 deg.C, the sample amount is 0.5ul, the initial temperature of the chromatographic column HP-5 is 80 deg.C, the temperature is raised to 250 deg.C by program of 10 deg.C/min, and the temperature is maintained for 10 min;
the conversion is calculated as: amount of unreacted dicyclopentadiene species/amount of dicyclopentadiene species added;
the specific method for calculating the conversion rate comprises the steps of firstly, preparing an external standard curve (external standard method) by using dicyclopentadiene with different concentrations, wherein the prepared standard curve is a straight line, the concentration of the dicyclopentadiene is used as a horizontal coordinate, and the area of a chromatographic peak is used as a vertical coordinate;
the area of dicyclopentadiene measured at regular time in the reaction process corresponds to the concentration of dicyclopentadiene on the standard curve, and the amount of dicyclopentadiene can be calculated, so that the conversion rate of dicyclopentadiene can be calculated.
The following method for quantitatively detecting tricyclodecanedicarboxylic acid comprises the following steps: determining by gas chromatography, wherein the detector is hydrogen flame detector, the chromatography conditions are that the sample inlet is 250 deg.C, the detector is 250 deg.C, the sample amount is 0.5ul, the initial temperature of the chromatographic column HP-5 is 80 deg.C, the temperature is raised to 250 deg.C by program of 10 deg.C/min, and the temperature is maintained for 10 min;
the formula for calculating the yield of tricyclodecanedicarboxylic acid is: amount of material of tricyclodecanedicarboxylic acid/amount of material of dicyclopentadiene;
the specific method for calculating the yield comprises the following steps: firstly, preparing an external standard curve (external standard method) by using the tricyclodecanedicarboxylic acid with different concentrations, wherein the prepared standard curve is a straight line, the concentration of the tricyclodecanedicarboxylic acid is used as an abscissa, and the area of a chromatographic peak is used as an ordinate;
the amount of tricyclodecanedicarboxylic acid can be calculated by measuring the area of tricyclodecanedicarboxylic acid at regular intervals during the reaction and by calculating the yield of tricyclodecanedicarboxylic acid (i.e., selectivity of tricyclodecanedicarboxylic acid) by using the concentration of tricyclodecanedicarboxylic acid on a standard curve.
Figure DEST_PATH_IMAGE004
As can be seen from Table 1, the cobalt rhodium manganese trimetal which is modified by phosphine ligand and loaded by alpha-alumina is used as the catalyst, the dicyclopentadiene can be efficiently catalyzed to synthesize the tricyclodecanedicarboxylic acid, the conversion rate of the dicyclopentadiene can reach more than 99%, and the selectivity of the tricyclodecanedicarboxylic acid can reach more than 92%. Therefore, the tricyclodecanedicarboxylic acid prepared by the method has high catalytic activity and good catalytic selectivity.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (9)

1. The preparation method of the tricyclodecanedicarboxylic acid is characterized by comprising the following steps: taking dicyclopentadiene as a raw material, taking cobalt rhodium manganese trimetal loaded on alpha-alumina modified by a phosphine ligand as a catalyst, controlling the pressure of mixed gas of synthesis gas and air to be 4-7MPa, the reaction temperature to be 150-170 ℃, the reaction pressure to be 7-9MPa, and reacting for 3-8h in the presence of an organic solvent, wherein the phosphine ligand comprises triphenylphosphine, tributylphosphine, triphenylphosphine oxide or triphenylphosphine sodium tri-metaphosphate;
the mass ratio of the phosphine ligand to the cobalt-rhodium-manganese trimetal loaded on the alpha-alumina is 1:3-1: 6;
the catalyst is prepared by the following steps: preparing cobalt rhodium manganese oxide supported by alpha-alumina, then carrying out hydrogenation reduction on the cobalt rhodium manganese oxide supported by the alpha-alumina to obtain cobalt rhodium manganese trimetal supported by the alpha-alumina, then carrying out phosphine ligand modification on the cobalt rhodium manganese trimetal supported by the alpha-alumina, wherein the phosphine ligand modification specifically comprises the steps of reacting the cobalt rhodium manganese trimetal supported by the alpha-alumina and a phosphine ligand in tetrahydrofuran for 0.5-2h, and then removing the tetrahydrofuran.
2. The method according to claim 1, wherein the organic solvent is toluene, n-hexane, or tetrahydrofuran.
3. The method according to claim 1 or 2, wherein the removal of tetrahydrofuran is carried out by removing tetrahydrofuran under vacuum at 20-45 ℃.
4. The method of claim 1 or 2, wherein the preparing of the alpha-alumina supported cobalt rhodium manganese oxide comprises the steps of: dissolving aluminum isopropoxide in ethanol, stirring and heating to 60-80 ℃ to obtain an ethanol solution of aluminum isopropoxide; dissolving manganese nitrate, cobalt chloride and rhodium trichloride in water, then adding the solution into an ethanol solution of aluminum isopropoxide, then adding a nitric acid solution, reacting at 60-80 ℃ for 24-72h, and roasting at 400-600 ℃ for 3-6 h.
5. The method of claim 3, wherein the step of preparing the alpha-alumina supported cobalt rhodium manganese oxide comprises the steps of: dissolving aluminum isopropoxide in ethanol, stirring and heating to 60-80 ℃ to obtain an ethanol solution of aluminum isopropoxide; dissolving manganese nitrate, cobalt chloride and rhodium trichloride in water, then adding the solution into an ethanol solution of aluminum isopropoxide, then adding a nitric acid solution, reacting at 60-80 ℃ for 24-72h, and roasting at 400-600 ℃ for 3-6 h.
6. The production method according to any one of claims 1, 2 or 5, wherein the hydrogenation reduction comprises the steps of: firstly reducing for 2-4h at the temperature of 400-600 ℃ in hydrogen, cooling to room temperature, then roasting for 3-6h at the temperature of 400-600 ℃ in air, and then reducing for 2-4h at the temperature of 600 ℃ in hydrogen.
7. The method according to claim 3, wherein the hydrogenation reduction comprises the steps of: firstly reducing for 2-4h at the temperature of 400-600 ℃ in hydrogen, cooling to room temperature, then roasting for 3-6h at the temperature of 400-600 ℃ in air, and then reducing for 2-4h at the temperature of 600 ℃ in hydrogen.
8. The method according to claim 4, wherein the hydrogenation reduction comprises the steps of: firstly reducing for 2-4h at the temperature of 400-600 ℃ in hydrogen, cooling to room temperature, then roasting for 3-6h at the temperature of 400-600 ℃ in air, and then reducing for 2-4h at the temperature of 600 ℃ in hydrogen.
9. The catalyst for catalyzing dicyclopentadiene to synthesize tricyclodecane dicarboxylic acid is characterized by comprising cobalt-rhodium-manganese trimetal loaded on phosphine ligand modified alpha-alumina;
the phosphine ligand comprises triphenylphosphine, tributylphosphine, triphenylphosphine oxide or triphenylphosphine sodium tri-meta-sulfonate;
the mass ratio of the phosphine ligand to the cobalt-rhodium-manganese trimetal loaded on the alpha-alumina is 1:3-1: 6;
the preparation method of the catalyst comprises the following steps:
preparing cobalt rhodium manganese oxide supported by alpha-alumina, then carrying out hydrogenation reduction on the cobalt rhodium manganese oxide supported by the alpha-alumina to obtain cobalt rhodium manganese trimetal supported by the alpha-alumina, then carrying out phosphine ligand modification on the cobalt rhodium manganese trimetal supported by the alpha-alumina, wherein the phosphine ligand modification specifically comprises the steps of reacting the cobalt rhodium manganese trimetal supported by the alpha-alumina and a phosphine ligand in tetrahydrofuran for 0.5-2h, and then removing the tetrahydrofuran.
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