CN113856720B - Heterogeneous hydroformylation catalyst and preparation method and application thereof - Google Patents

Heterogeneous hydroformylation catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN113856720B
CN113856720B CN202010613655.1A CN202010613655A CN113856720B CN 113856720 B CN113856720 B CN 113856720B CN 202010613655 A CN202010613655 A CN 202010613655A CN 113856720 B CN113856720 B CN 113856720B
Authority
CN
China
Prior art keywords
catalyst
product
reaction
cobalt
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010613655.1A
Other languages
Chinese (zh)
Other versions
CN113856720A (en
Inventor
何岩
石滨
田博
边路路
周锐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202010613655.1A priority Critical patent/CN113856720B/en
Publication of CN113856720A publication Critical patent/CN113856720A/en
Application granted granted Critical
Publication of CN113856720B publication Critical patent/CN113856720B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/394—
    • B01J35/50—
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention provides a heterogeneous hydroformylation catalyst, and a preparation method and application thereof. The catalyst is in a rhodium (Rh)/(CoO-CuO) -N-CNTs structure form, and is prepared by adopting the process steps of oxidizing roasting, catalytic carbonization and the like. When the catalyst is used for the heterogeneous catalysis hydroformylation reaction, the catalyst has high stability and high dispersibility, and a product with high conversion rate and high selectivity can be obtained.

Description

Heterogeneous hydroformylation catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a heterogeneous hydroformylation catalyst, and a preparation method and application thereof.
Background
Utilizing the olefin and synthesis gas resources produced in large quantities in petrochemical and coal chemical industries, the olefin reacts with the synthesis gas under the action of homogeneous Co or Rh metal organic catalyst to prepare aldehyde, and the reaction is called hydroformylation or OXO reaction. Since the discovery of the OXO technology in 1938, the development of the technology is long-lasting within 60 years of the 20 th century, and the cost-effective n-butyraldehyde and isobutyraldehyde obtained by propylene through the OXO technology and alcohol and ester products prepared by deep processing, particularly plasticizers, have millions of tons of consumption every year in the world. The OXO technology is a relatively mature technology system.
Since the 21 st century, the research on hydroformylation technology has advanced, and the substrates are expanding, from the original linear olefins to cycloolefins, unsaturated functional compounds, alcohols, epoxides, etc., and new catalyst ligands are developed, and the reaction or selectivity is further improved.
However, it should be seen that while the OXO technology has made a great progress, the prior art still has unsatisfied places, which mainly shows that the mainstream industrial catalyst in the prior art is still a homogeneous metal organic catalyst, such as a catalytic system of precious metal Rh-triphenylphosphine commonly used in the OXO industrial plant of propylene, and needs to use a ligand with the same high price, so that the catalyst is difficult to separate and recycle, has poor thermal stability and is high in cost, and further reduction of the plant economy is restricted. Researchers have developed liquid-liquid heterogeneous OXO catalysis technology, particularly temperature-induced phase change catalysis systems developed in recent years, and on the premise of ensuring reaction effects close to those of homogeneous catalysts, the difficulty of catalyst separation and circulation is greatly reduced, but the maturity of the existing technology is far from the gap of industrial application. The solid heterogeneous catalyst can completely overcome the problems that the existing homogeneous catalyst is difficult to separate and recycle, is easy to run off, and causes high production cost and the like theoretically. However, the activity and stability required by industrial application cannot be achieved by the prior disclosed heterogeneous catalysts, or the cost is more expensive, so that the industrial popularization is restricted.
Disclosure of Invention
Aiming at the problems of the existing hydroformylation technology, the invention aims to provide a heterogeneous hydroformylation catalyst which has high stability, high activity caused by high dispersity and low cost.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the catalyst is in a structural form of rhodium (Rh)/(CoO-CuO) -N-CNTs, wherein Rh is an active center, and (CoO-CuO) -N-CNTs are carriers, coO-CuO in the carriers is cobalt oxide and copper oxide eutectic nano particles, and N-CNTs are macroporous nitrogen modified carbon nano tube materials.
Heterogeneous catalysis of an OXO homogeneous catalyst is a known problem in the industry, and researchers use carbon materials such as activated carbon and the like to load rhodium by a traditional method as a catalyst for OXO reaction. However, the acting force between Rh and C is weak, the adsorption is not strong, rh is easy to lose, and the level of industrial application is not reached so far. According to the known knowledge that nitrogen atoms have 7 electrons and carbon atoms have 6 electrons, the nitrogen-doped carbon material can effectively improve the electronic characteristics of the carbon material. The traditional physical doping mode has the problems of uneven distribution of nitrogen sources, weak bonding force with carbon materials, loose structure, easy loss and the like. The catalytic precursor obtained by the method disclosed by the invention is a nitrogen-containing organic polymer, and because the in-situ reaction introduction of a nitrogen source and the specific treatment mode are adopted, the surface of the catalyst is rich in a large number of nitrogen-containing functional groups which are distributed more uniformly, and metal atoms can be anchored more stably and more effectively. However, the inventors have found in actual studies that rhodium can be anchored effectively and hardly lost by direct nitrogen-modified carbon material anchoring of rhodium, but the catalyst activity is low and the reaction selectivity is not high, because the interaction force between Rh and N is too strong, which affects the performance of the catalytic action of rhodium.
Co atoms are introduced in situ to prepare highly dispersed CoO-N-CNTs, and are firmly anchored by utilizing the strong interaction between Co and N. Meanwhile, by utilizing proper interaction force between Rh-CoO, the high dispersion and high-efficiency utilization of Rh atoms can be realized, and the activity and selectivity of the catalyst are ensured.
CN106362766 discloses a method for preparing Rh-CoO catalyst, but the inventor does not show similar catalytic activity with propylene when using the catalyst to research the OXO reaction of cyclooctadiene, and the catalytic activity is far lower than that of Rh-CoO-NNTs catalyst in the invention. The reason for this is that the synergistic effect of Rh-CoO and Rh-NNTs exists in Rh-CoO-NNTs, so that the activity and stability of the catalyst exceed the effect of the two schemes which are implemented independently.
The inventor also surprisingly finds that the introduction of CuO can further remarkably improve the activity of the catalyst by 2 to 5 times on the premise of maintaining the approximately same selectivity. Because the atomic sizes of Cu and Co are close, under the well-designed synthesis condition, the Cu and the Co can enter into the crystal lattice of the other to obtain a CoO-CuO eutectic structure, thereby improving the electronic property, increasing the surface active sites and obviously improving the activity of the catalyst.
In the present invention, the mass ratio of Rh atoms to Co atoms in the catalyst is 1: (50-500), the molar ratio of Cu to Co is (0.05-0.5): 1, preferably (0.05-0.2): 1. The rhodium atom is the active center of the catalyst, the most key technology of the invention is that through the elaborately designed conditions, the rhodium atom can be highly dispersed or even dispersed in the form of a single atom and firmly anchored on the surface of the nano CoO/CuO nano particles, and the stability of the Rh single atom can be ensured through the interaction with proper strength between the rhodium atom and the nano CoO, so that the maximum utilization of the Rh atom is realized, and the catalytic activity of the Rh atom in the active center is ensured. 1: the mass ratio of rhodium atoms to Co atoms of (50-500) can ensure that Rh atoms are anchored on the surface of the nano CoO in a state of being dispersed as much as possible or even in a monoatomic state.
In the invention, the cobalt element is from organic cobalt salt and/or inorganic cobalt salt; preferably, the inorganic cobalt salt is one or more of cobalt chloride, cobalt fluoride, cobalt sulfate and cobalt sulfonate, and the organic cobalt salt is one or more of cobalt formate, cobalt acetate and cobalt acetylacetonate, preferably cobalt acetylacetonate.
In the invention, the copper element is derived from a copper salt, preferably the copper salt is one or more of copper formate, copper acetate and copper acetylacetonate, and more preferably the copper acetylacetonate.
It is another object of the present invention to provide a method for preparing the catalyst.
The preparation method of the catalyst adopts the processes of oxidizing roasting and catalytic carbonization.
In the invention, the preparation method of the catalyst comprises the following steps:
s1: mixing paraformaldehyde and phenol and reacting;
s2: mixing paraformaldehyde and melamine for reaction;
s3: adding the S2 reaction product, cobalt salt and copper salt into the S1 reaction product for continuous reaction;
s4: adding silica gel into the reaction product of S3, stirring and mixing, and oxidizing and roasting;
s5: catalyzing and carbonizing the S4 oxidized and roasted product;
s6: s5, treating a catalytic carbonization product with alkali liquor, adjusting the pH value, removing water, drying, crushing and screening;
s7: and (3) putting the product of the S6 into a sodium hexachlororhodate solution, stirring and mixing, removing water, and drying in vacuum to obtain the target product.
In the invention, the molar ratio of paraformaldehyde to phenol in S1 is (2-5): 1, and the paraformaldehyde is calculated by the mole number of formaldehyde.
In the invention, the reaction atmosphere in the S1 is oxygen-free.
In the invention, the reaction temperature in the S1 is 40-80 ℃.
In the present invention, the pH value during the reaction in S1 is 11 to 12.
In the invention, the reaction time in the S1 is 0.5-5 h.
In the invention, the molar ratio (1-2) of paraformaldehyde to melamine in S2 is 1, and the paraformaldehyde is calculated by the mole number of formaldehyde.
In the invention, the reaction temperature in the S2 is 70-90 ℃.
In the present invention, the pH value during the reaction in S2 is 11 to 12.
In the invention, the reaction time in the S2 is 1-2 h.
In the present invention, the mass ratio of the S1 product to the S2 product added to S3 is (0.5-2): 1, and preferably the mass ratio of the S1 product to the S2 product is (0.5-1): 1. The proportion ensures the full phenolic aldehyde condensation reaction, the full introduction of nitrogen element and proper proportion. In order to ensure enough number of active centers of Co atoms, and ensure that Co is fully dispersed without agglomeration, thereby reducing the utilization rate of Co atoms.
In the invention, the total mass of the cobalt salt and the copper salt added in the S3 is 0.1-10%, preferably 0.5-5% of the total mass of the S1 product and the S2 product.
In the invention, the reaction temperature in the S3 is 70-90 ℃.
In the invention, the reaction time in the S3 is 30-60min.
In the invention, the adding amount of the silica gel in the S4 is 20-200% of the mass of the S3 product, preferably 50-150%, and most preferably 80-120%. The nitrogen modified carbon material prepared by the prior disclosed technology generally has wide pore channel distribution, a large number of 1-20 nm mesopores, and the problems of wide pore channel distribution, low selectivity, large diffusion resistance in the catalyst, low catalyst activity and the like in the catalytic reaction. In the invention, a more uniform pore channel structure, particularly a macroporous structure, can be obtained by introducing silica gel with a specific size and then forming pores by using an alkali etching silica gel method, so that the diffusion resistance in the catalyst is obviously reduced and the catalytic activity is improved.
In the present invention, the silica gel particle size in S4 is 2 to 100nm, preferably 5 to 50nm. The introduction of silica gel has a key influence on the pore structure of the final catalyst, and the proper particle size is matched with the optimized roasting process, so that the proper size and structure of the catalyst pore can be obtained, the mechanical strength and the proper specific surface area of the catalyst are ensured, the final heterogeneous catalyst structurally has a large amount of mesoporous structures, and the diffusion and mass transfer of reaction raw materials and products are utilized. The silica gel added in S4 is finally removed by alkali etching, the concentration and the adding mode of the alkali liquor are carefully selected, and the alkali with lower concentration is preferably slowly removed at lower temperature. Too fast alkalifying speed and too fast reaction easily cause too wide size distribution of catalyst channels and even cause collapse of the catalyst channels.
In the invention, the roasting temperature in S4 is 150-500 ℃, preferably 180-300 ℃.
In the invention, the roasting time in the S4 is 2-24h.
In the invention, the roasting atmosphere in S4 contains 1-50% of oxygen, preferably 5-20%.
The oxidizing roasting is a key step for obtaining the required specific nitrogen modified group, nano cobalt oxide and copper oxide eutectic nano particles, the nitrogen modified group, the structure and the quantity of the cobalt oxide and copper oxide eutectic nano particles can be influenced by overhigh oxygen content and overhigh temperature, and further the interaction of the nitrogen modified group, metal and metal oxide is influenced, so that the metal is easy to lose, and the service life of the catalyst is shortened. After oxidizing roasting, a large amount of eutectic nano particles of cobalt oxide and copper oxide with nitrogen-containing ring structures, sheet shapes and spheres are obtained, the size of the eutectic particles is 2-100nm, generally 5-20nm, the eutectic particles are highly dispersed metal oxides, and the structural strength and the dispersion degree of active centers of the final carbon material are obviously improved.
In the invention, the catalytic carbonization temperature in S5 is 500-1200 ℃, preferably 500-1000 ℃, more preferably 600-800 ℃, and most preferably a finely selected temperature programming process is adopted.
In the invention, the carbonization time in S5 is 12-24h.
In the invention, the atmosphere in the S5 is absolute oxygen.
In order to obtain the required nitrogen modified carbon nanotube structure, the roasting temperature must be carefully selected in the roasting carbonization process, and the nitrogen modified carbon material prepared by the prior disclosed technology generally needs higher temperature, but the excessively high temperature can destroy the carbon nanotube structure and cause the metal oxide crystal lattice to agglomerate and grow up, reduce or completely lose the catalytic activity. The inventors have surprisingly found that the introduction of cobalt and copper salts in the form of cobalt acetylacetonate and copper acetylacetonate during the in situ synthesis of the modified phenolic resin can significantly reduce the carbonization temperature. Because the cobalt salt and the ketone salt which are introduced in situ in the phenolic resin synthesis process obtain highly dispersed active centers of cobalt and copper, highly dispersed nano CoO/CuO eutectic particles are obtained after oxidizing roasting, and play roles of catalytic deoxidation and carbonization in the carbonization process. The metal oxide has catalytic deoxidation and dehydration functions and is a known technology, but the highly dispersed nano CoO/CuO eutectic particles are introduced and prepared in the form of organic cobalt salt and copper salt, so that the catalytic deoxidation and carbonization activities are remarkably improved, and the carbonization temperature can be remarkably reduced. The above-mentioned baking temperature can obtain the required carbon nanotube structure and nano-CoO structure to the maximum extent, so that it can provide larger specific surface area and more centre for anchoring Co atom. After oxidation roasting and catalytic carbonization treatment, organic nitrogen exists in the interior and on the surface of an inner pore channel of the catalyst in various forms, such as pyridine nitrogen, pyrrole nitrogen, graphitized nitrogen and the like, and a proper roasting process can obtain a proper organic nitrogen form and a larger proportion of surface organic nitrogen functional groups to the maximum extent, so that Co atoms can be anchored better.
In the invention, the alkali liquor in the S6 is NaOH aqueous solution.
In the invention, the S5 product is treated in NaOH aqueous solution with the concentration of 2 percent for 12 to 24 hours.
In the invention, the S6 is continuously treated by deionized water with 10-100 times volume of NaOH aqueous solution until the pH value of the water phase reaches neutrality.
In the present invention, the concentration of the sodium hexachlororhodate aqueous solution in S7 is 1 to 10mg/ml.
In the invention, the S7 is stirred and mixed for 2-12 h at room temperature.
In the invention, the vacuum drying is carried out for 2-24h in the S7.
It is a further object of the present invention to provide a use of said catalyst.
A use of the catalyst. The catalyst is used for heterogeneous catalysis hydroformylation reaction; preferably, the heterogeneously catalyzed hydroformylation is the hydroformylation of a heterogeneously catalyzed cyclooctadiene.
Optionally, the catalytic hydroformylation reaction product is subjected to ozonization, ammoniation and hydrogenation reactions to prepare the triamine.
Optionally, the triamine is continued to produce triisocyanate via photochemical reactions.
The above-described route for the preparation of triisocyanates is illustrated below:
Figure BDA0002561341840000081
in the present invention, the reaction temperature for the hydroformylation of cyclooctadiene is 50 to 200 ℃, preferably 140 to 180 ℃.
In the present invention, the reaction pressure for the cyclooctadiene hydroformylation is 3 to 30MPa, preferably 6 to 18MPa.
In the present invention, the reaction time for the cyclooctadiene hydroformylation is 1 to 16 hours, preferably 2 to 6 hours.
In some embodiments, the cyclooctadiene is a product of the cyclic oligomerization of 1, 3-butadiene, and may also be a by-product of Cyclododecatriene (CDT) from 1, 3-butadiene. The triisocyanate has a plurality of NCO functional groups, so the triisocyanate has wide application potential in the fields of polyurethane coatings, elastomers, modified products and the like. If the by-product cyclooctadiene of CDT is utilized, the triisocyanate can be prepared with outstanding cost advantages.
The invention has the positive effects that:
(1) By adopting the non-catalyst, the single-step reaction yield and the total yield are high, the number of byproducts and three wastes is small, the conversion rate can reach more than 90 percent, and the selectivity is 84 to 89 percent;
(2) When the catalyst is used for heterogeneous catalysis hydroformylation reaction, the catalyst has high stability and high dispersity.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The raw materials are as follows:
a-15 ion exchange resins from Dow, 1, 5-cyclooctadiene, syngas, naOH, phenol, chlorobenzene, methanol, ammonia, hydrogen, and phosgene from Wanhua; silica gel: qingdao ocean corporation; other main raw materials are from the alatin reagent company and have the following specifications:
1, 5-cyclooctadiene: the purity is 98 percent;
synthesis gas: CO and H 2 Molar ratio 1<1ppm；
NaOH: a 2% aqueous solution;
phenol: 99.5 percent;
methanol: 99.5 percent;
chlorobenzene: 99 percent;
ammonia: 99 percent;
silica gel: analyzing and purifying;
ethylene glycol: analyzing and purifying;
cobalt acetylacetonate: 98 percent;
copper acetylacetonate: 98 percent;
m-cresol: analyzing and purifying;
melamine: analyzing and purifying;
sodium hexachlororhodate: 90 percent.
The GC analysis method used is illustrated below:
gas chromatograph: shimadzu GC-2010PLUS, column: DB-5MS (30m 0.25mm 0.25 μm);
gas chromatography conditions:
carrying high-purity nitrogen gas with high gas purity,
the hydrogen flow rate is 30ml/min,
the air flow rate is 300ml/min,
the flow rate of the make-up air is 25ml/min,
the constant flow is carried out in a sample injection mode,
the temperature of the vaporization chamber is 280 ℃,
the split ratio is 30/1, and the material is,
the column flow rate was 1.5ml/min,
the initial column temperature is 100 ℃, the temperature is kept for 0.5 minute, the temperature is raised to 160 ℃ at 15 ℃/min, the temperature is kept for 1.5 minutes, the temperature is raised to 260 ℃ at 20 ℃/min, the temperature is kept for 9 minutes,
the temperature of the detector is 280 c,
sample introduction: 1 mu l of the mixture is added into the reaction kettle,
integration conditions: the slope is 2000, the minimum peak area is 200, and the area percentage content of a certain substance is calculated as follows:
Figure BDA0002561341840000111
wherein C is the area percentage content of the substance in the sample, A is the peak area of the substance in the sample, and Atotal is the sum of the peak areas of all peaks with solvent peaks subtracted.
Comparative example 1
Preparation of Rh/CoO-NCTs catalyst A.
Preparation of 5g of catalyst A:
s1: paraformaldehyde (in terms of mole of formaldehyde) and phenol are fully mixed according to the molar ratio of 5 to 1, and the mixture is reacted for 1 hour under the conditions of no oxygen, 80 ℃ and pH value of 12.
S2: paraformaldehyde (in moles of formaldehyde) and melamine were reacted at a molar ratio of 1.
S3: controlling the mass ratio of the S1 product to the S2 product to be 0.5, adding the product of the step S2 and cobalt acetylacetonate accounting for 10% of the total mass into the reaction product of the S1, fully mixing, and keeping the temperature at 80 ℃ to continue reacting for 60min to obtain a high polymer precursor.
S4: adding silica gel powder with the particle size of 50nm into the reaction product of the S3 according to the mass ratio of 1; at O 2 N content 5% 2 Oxidizing and roasting at 300 ℃ in atmosphere12h。
S5: the product of S4 is in N 2 And (5) roasting for 24 hours under the protection and 700 ℃.
S6: and (3) treating the roasted product in 2% NaOH aqueous solution for 24 hours, then treating the roasted product with deionized water with the volume of 100 times that of the NaOH aqueous solution until the pH value of the water phase is neutral, and centrifuging and separating the water phase by a centrifugal machine at 2000 rpm. The obtained product is dried, crushed and sieved to obtain the particle size of 10-100 microns.
S7: preparing an aqueous solution of sodium hexachlororhodate with the concentration of 2mg/ml, placing a product of S6 in the solution, controlling the mass ratio of Rh to Co to be 1.
Comparative example 2
Catalyzing the formylation of cyclooctadiene.
1g of the catalyst A prepared in comparative example 1 was charged into a 500ml autoclave, 150g of 1, 5-cyclooctadiene and 150g of chlorobenzene solvent were added, and the reaction was carried out at 140 ℃ for 16 hours while maintaining the synthesis gas pressure at 8MPa. A sample was taken for GC analysis and 1, 5-cyclooctadiene conversion was 50% with a 4-carbonylmethyl-cyclooctene selectivity of 84%.
Example 1
Preparation of Rh/CoO-CuO-NCTs catalyst B.
Preparation of 5g of catalyst B:
the same as comparative example 1 except that cobalt acetylacetonate in S3 was changed to a mixture of equal amounts of cobalt acetylacetonate and copper acetylacetonate, and the molar ratio of cobalt to copper was controlled to 10.
Example 2
Catalyzing the formylation of cyclooctadiene.
1g of the catalyst B prepared in example 1 was charged into a 500ml autoclave, 150g of 1, 5-cyclooctadiene and 150g of chlorobenzene solvent were added, and the reaction was carried out at 140 ℃ for 16 hours while maintaining the synthesis gas pressure at 8MPa. A sample was taken for GC analysis and 1, 5-cyclooctadiene conversion was 90% and 4-carbonylmethyl-cyclooctene selectivity was 89%.
Example 3
Preparation of Rh/CoO-CuO-NCTs catalyst C.
Preparation of 5g of catalyst C:
the method is the same as example 1, except that S3 controls the mass ratio of the S1 product to the S2 product to be 1; in addition, S7 controls the mass ratio of Rh to Co to be 1.
Example 4
Catalyzing the formylation of cyclooctadiene.
1g of the catalyst C prepared in example 3 was charged into a 500ml autoclave, 150g of 1, 5-cyclooctadiene and 150g of chlorobenzene solvent were added, and the reaction was carried out at 180 ℃ for 6 hours while maintaining the synthesis gas pressure at 18MPa. A sample was taken for GC analysis and showed 92% conversion of 1, 5-cyclooctadiene and 88% selectivity to 4-carbonylmethyl-cyclooctene.
Comparative example 3
Preparation of Rh/-NCTs catalyst D without oxide eutectic nanoparticles.
Preparation of 5g of catalyst D:
s1: paraformaldehyde (in terms of mole of formaldehyde) and phenol are fully mixed according to the molar ratio of 5 to 1, and the mixture is reacted for 1 hour under the conditions of no oxygen, 80 ℃ and pH value of 12.
S2: paraformaldehyde (in moles of formaldehyde) and melamine were reacted at a molar ratio of 1.
S3: and then adding the product S2 into the reaction product of the step S1, wherein the mass ratio of the products S1 and S2 is 2.
S4: adding silica gel powder with the particle size of 50nm into the reaction product of the S3 according to the mass ratio of 1; at O 2 N content 5% 2 Oxidizing and roasting for 12 hours at 300 ℃ in the atmosphere.
S5: oxidizing the roasted product in N 2 And (5) roasting for 24 hours under the protection and 700 ℃.
S6: and (3) treating the roasted product in 2% NaOH aqueous solution for 24 hours, then treating the roasted product with deionized water with the volume being 100 times that of the NaOH aqueous solution until the pH value of a water phase is neutral, and centrifuging and separating the treated product by a centrifugal machine at 2000 rpm. The obtained product is dried, crushed and sieved to obtain the particle size of 10-100 microns.
S7: preparing an aqueous solution of sodium hexachlororhodate with the concentration of 2mg/ml, putting the product of S6 into the solution, fully stirring and mixing for 12 hours at room temperature, then centrifugally dewatering at 2000 r/min, and drying for 24 hours under the vacuum condition to obtain the target product.
Comparative example 4
The hydroformylation of cyclooctadiene was catalyzed with Rh/-NCTs catalyst D without oxide eutectic nanoparticles.
1g of the catalyst D prepared in comparative example 3 was charged into a 500ml autoclave, 150g of 1, 5-cyclooctadiene and 150g of chlorobenzene solvent were added, and the reaction was carried out at 180 ℃ for 16 hours while maintaining the synthesis gas pressure at 18MPa. A sample was taken for GC analysis and showed 12% conversion of 1, 5-cyclooctadiene and 71% selectivity to 4-carbonylmethyl-cyclooctene.
Comparative example 5
And (3) preparing the Rh/CoO catalyst E without the macroporous nitrogen modified carbon nano tubes.
Preparation of 5g of catalyst E:
mixing cobalt acetylacetonate, ethylene glycol and deionized water at normal temperature, wherein the mass ratio of the cobalt acetylacetonate to the ethylene glycol is 95. Cooling the product to room temperature, centrifuging at centrifuge speed of 10,000 rpm for 7min, ultrasonically washing with methanol for 1min, and repeating centrifuging and washing for 5 times. And drying the product at 52 ℃ in vacuum for 12h to obtain the nano CoO serving as a carrier for later use. The CoO and deionized water are mixed according to the volume ratio of 95. And centrifuging the product at 10000 r/min for 5min, ultrasonically washing for 1min by using methanol, repeatedly centrifuging and washing for 5 times, and vacuum-drying at 52 ℃ for 12h to obtain the target product.
Comparative example 6
And catalyzing the cyclooctadiene formylation by using an Rh/CoO catalyst E which does not contain the macroporous nitrogen modified carbon nano tubes.
0.2g of the catalyst E prepared in comparative example 5 was taken, charged into a 500ml autoclave, and charged with 150g of 1, 5-cyclooctadiene and 150g of chlorobenzene solvent, and reacted at 180 ℃ for 16 hours while maintaining the synthesis gas pressure at 18MPa. A sample was taken for GC analysis and 1, 5-cyclooctadiene conversion was 17% with a selectivity to 4-carbonylmethyl-cyclooctene of 84%.
Example 5
Further preparing amine and isocyanate.
4-Carbonylmethyl-cyclooctene prepared in example 2, in a tubular reaction with O and a diameter of 20mm 2 /O 3 The mixed gas is fully contacted and reacts, O 2 /O 3 From an ozone generator, O 3 The concentration is about 10%, the reaction temperature is-5 ℃, the gas-liquid pseudo-flow is carried out, the 4-carbonyl methyl-cyclooctene and water are fed into a reaction tube according to the mass ratio of 1. The 4-carbomethyl-cyclooctene was oxidized to 4-carbomethyl-1, 8-octanediol with a selectivity of 90%.
1.0g of 4-carbonylmethyl-1, 8-octanediol was charged into a 500ml pressurized reactor, and NH was added 3 200g, and 10g of Dow A-15 catalyst, using N 2 The reaction was carried out at 80 ℃ for 2h while maintaining the pressure at 2 MPa. Removing unreacted ammonia from ammoniated product, adding into 500ml high pressure reaction kettle, adding 200g methanol as solvent, 1g NaOH flake alkali as adjuvant, and 5g Raney nickel as catalyst, maintaining H 2 Reacting for 4 hours under the pressure of 16MPa to obtain the corresponding triamine, and carrying out ammoniation and reduction with the total selectivity of 92 percent.
The corresponding triisocyanates can be prepared from the triamines by phosgenation, and the technology adopted is a mature technology of the metric system in the industry and is not described in detail here.
It will be appreciated by those skilled in the art that modifications and adaptations to the invention may be made in light of the teachings of the present disclosure. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.

Claims (26)

1. The high-stability high-dispersity heterogeneous hydroformylation catalyst is characterized in that the catalyst is rhodium (Rh)/(CoO-CuO) -N-CNTs in a structural form, wherein Rh is an active center, and (CoO-CuO) -N-CNTs is a carrier, coO-CuO in the carrier is cobalt oxide and copper oxide eutectic nano particles, and N-CNTs is a macroporous nitrogen modified carbon nano tube material.
2. The catalyst according to claim 1, wherein the mass ratio of Rh atoms to Co atoms in the catalyst is 1: (50-500) and the molar ratio of Cu to Co is (0.05-0.5): 1.
3. The catalyst of claim 2, wherein the molar ratio of Cu to Co in the catalyst is (0.05-0.2): 1.
4. The catalyst according to claim 1 or 2, wherein the cobalt element is derived from an organic cobalt salt and/or an inorganic cobalt salt.
5. The catalyst of claim 4, wherein the inorganic cobalt salt is one or more of cobalt chloride, cobalt fluoride, cobalt sulfate and cobalt sulfonate, and the organic cobalt salt is one or more of cobalt formate, cobalt acetate and cobalt acetylacetonate.
6. The catalyst of claim 5 wherein the organo cobalt salt is cobalt acetylacetonate.
7. The catalyst according to claim 1 or 2, wherein the copper element is derived from a copper salt.
8. The catalyst of claim 7, wherein the copper salt is one or more of a copper formate, a copper acetate, and a copper acetylacetonate.
9. The catalyst according to claim 8, wherein the copper salt is copper acetylacetonate.
10. A method for preparing the catalyst according to any one of claims 1 to 9, wherein an oxidative roasting and catalytic carbonization process is used, and the preparation method comprises the following steps:
s1: mixing paraformaldehyde and phenol and reacting;
s2: mixing paraformaldehyde and melamine for reaction;
s3: adding the reaction product of S2, cobalt salt and copper salt into the reaction product of S1 for continuous reaction;
s4: adding silica gel into the reaction product of S3, stirring and mixing, and oxidizing and roasting;
s5: heating the S4 oxidized and roasted product for catalytic carbonization;
s6: s5, treating a catalytic carbonization product with alkali liquor, adjusting the pH value, removing water, drying, crushing and screening;
s7: and (3) putting the product of the S6 into a sodium hexachlororhodate solution, stirring and mixing, and dehydrating and vacuum-drying to obtain the target product.
11. The preparation method according to claim 10, wherein the molar ratio of paraformaldehyde to phenol in S1 is (2-5): 1, and the paraformaldehyde is calculated by the mole of formaldehyde;
and/or the reaction atmosphere is oxygen-free;
and/or the reaction temperature is 40-80 ℃;
and/or the pH value during the reaction is 11-12;
and/or the reaction time is 0.5-5 h.
12. The preparation method according to claim 10, wherein the molar ratio of paraformaldehyde to melamine in S2 (1-2) is 1, and the paraformaldehyde is calculated by the mole of formaldehyde;
and/or the reaction temperature is 70-90 ℃;
and/or the pH value during the reaction is 11-12;
and/or the reaction time is 1-2 h.
13. The method according to claim 10, wherein the mass ratio of the S1 product to the S2 product added to S3 is (0.5-2): 1;
and/or the total mass of the added cobalt salt and the copper salt is 0.1-10% of the total mass of the added S1 product and S2 product;
and/or the reaction temperature is 70-90 ℃;
and/or the reaction time is 30-60min.
14. The method according to claim 13, wherein the mass ratio of the S1 product to the S2 product added to S3 is (0.5-1): 1;
and/or the total mass of the added cobalt salt and copper salt is 0.5-5% of the total mass of the added S1 product and S2 product.
15. The preparation method according to claim 10, wherein the amount of silica gel added in the S4 is 20-200% of the mass of the S3 product;
and/or the particle size of the silica gel is 2-100 nm;
and/or, the roasting temperature is 150-500 ℃;
and/or the roasting time is 2-24h;
and/or, the roasting atmosphere contains 1-50% of oxygen.
16. The preparation method according to claim 15, wherein the amount of the silica gel added in the S4 is 50-150% of the mass of the S3 product;
and/or the particle size of the silica gel is 5-50 nm;
and/or, the roasting temperature is 180-300 ℃;
and/or the roasting atmosphere contains 5 to 20 percent of oxygen.
17. The preparation method according to claim 16, wherein the amount of silica gel added in the S4 is 80-120% of the mass of the S3 product.
18. The preparation method according to claim 10, wherein the catalytic carbonization temperature in S5 is 500 to 1200 ℃;
and/or the carbonization time is 12-24h;
and/or the atmosphere is oxygen-free.
19. The method according to claim 18, wherein the catalytic carbonization temperature in S5 is 500 to 1000 ℃.
20. The method according to claim 19, wherein the catalytic carbonization temperature in S5 is 600 to 800 ℃.
21. The preparation method of claim 10, wherein the S6 medium alkali solution is NaOH aqueous solution;
and/or treating the S5 product in a NaOH aqueous solution with the concentration of 2% for 12-24h;
and/or continuously treating with deionized water with 10-100 times volume of NaOH aqueous solution until the pH value of the water phase reaches neutrality.
22. The preparation method of claim 10, wherein the concentration of the aqueous solution of sodium hexachlororhodate in S7 is 1 to 10mg/ml;
and/or stirring and mixing for 2-12 h at room temperature;
and/or, vacuum drying for 2-24h.
23. Use of a catalyst according to any one of claims 1 to 9 or a catalyst prepared by a preparation process according to any one of claims 10 to 22 for heterogeneously catalyzed hydroformylation.
24. The use of a catalyst according to claim 23, wherein the heterogeneously catalyzed hydroformylation reaction is the hydroformylation of a heterogeneously catalyzed cyclooctadiene;
optionally, the catalytic hydroformylation reaction product is subjected to ozonization, ammoniation and hydrogenation to prepare a triamine;
optionally, the triamine is continued to produce triisocyanate via photochemical reactions.
25. The use of a catalyst according to claim 24, wherein the reaction temperature of cyclooctadiene hydroformylation is 50-200 ℃;
and/or the reaction pressure is 3-30MPa;
and/or the reaction time is 1-16 h.
26. Use of a catalyst according to claim 25, characterised in that the reaction temperature of the cyclooctadiene hydroformylation is 140-180 ℃;
and/or the reaction pressure is 6-18 MPa;
and/or the reaction time is 2-6 h.
CN202010613655.1A 2020-06-30 2020-06-30 Heterogeneous hydroformylation catalyst and preparation method and application thereof Active CN113856720B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010613655.1A CN113856720B (en) 2020-06-30 2020-06-30 Heterogeneous hydroformylation catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010613655.1A CN113856720B (en) 2020-06-30 2020-06-30 Heterogeneous hydroformylation catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113856720A CN113856720A (en) 2021-12-31
CN113856720B true CN113856720B (en) 2022-11-08

Family

ID=78981257

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010613655.1A Active CN113856720B (en) 2020-06-30 2020-06-30 Heterogeneous hydroformylation catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113856720B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115646547B (en) * 2022-11-22 2024-01-30 中国石油大学(华东) Rhodium-cobalt loaded monoatomic alloy catalyst for hydroformylation of high-carbon olefin and preparation and application methods thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104056622B (en) * 2013-03-20 2017-02-08 中国科学院大连化学物理研究所 Rhodium/carbon nanotube catalyst and preparation method and application
CN103288416B (en) * 2013-05-27 2015-10-21 东华大学 A kind of modified 3 D fiber base aerogel material and preparation method thereof
CN106362766B (en) * 2016-08-04 2018-11-20 中国科学技术大学先进技术研究院 A kind of Rh/CoO nanocatalyst and preparation method thereof, application
CN111097416A (en) * 2020-01-14 2020-05-05 中国科学院兰州化学物理研究所 Preparation of carbon-supported cobalt heterogeneous catalyst and application of carbon-supported cobalt heterogeneous catalyst in catalyzing hydroformylation reaction of olefin

Also Published As

Publication number Publication date
CN113856720A (en) 2021-12-31

Similar Documents

Publication Publication Date Title
KR20160080379A (en) Rh-C3N4 Heterogeneous catalyst for acetic acid synthesis by carbonylation reaction
CN113856720B (en) Heterogeneous hydroformylation catalyst and preparation method and application thereof
CN109847804B (en) Phenolic hydroxyl modified polystyrene immobilized rhodium-phosphine complex catalyst and preparation method and application thereof
CN111732097A (en) Preparation method and application of large-specific-surface-area graphitized carbon
CN111097416A (en) Preparation of carbon-supported cobalt heterogeneous catalyst and application of carbon-supported cobalt heterogeneous catalyst in catalyzing hydroformylation reaction of olefin
CN112973746A (en) Preparation method of supported vanadium phosphorus oxygen catalyst, catalyst prepared by preparation method and application of catalyst
CN113751040A (en) Nitrogen-doped carbon-silicon composite material loaded cobalt-copper bimetallic catalyst and preparation method and application thereof
CN107930647B (en) Catalyst, preparation method thereof and preparation method of 2-ethylhexanal
CN110813281B (en) Application of nano-carbon supported cluster-state palladium-based catalyst in preparation of primary amine by catalytic hydrogenation of nitrile compound
CN104289222A (en) CuO-loaded SiO2 catalyst applied to preparation of benzenediol and benzoquinone and preparation method of catalyst
CN109529879B (en) PdNi/RGO nano-catalyst and preparation method thereof
CN109395784B (en) Preparation and application of metal catalyst supported by phenolic resin modified carrier
KR20170007636A (en) Catalysts for preparing Olefin by Dehydrogenation of Hydrocarbon, and Preparation Method Thereof
CN111545239B (en) Solid catalyst for glycerol oxidation and preparation method thereof
CN111167515B (en) Monomolecular heteropoly acid inlaid honeycomb-shaped carbon material loaded nano metal catalyst and preparation method and application thereof
CN113042083A (en) Palladium-based monatomic catalyst and preparation and application methods thereof
CN112403521B (en) Polyacid catalyst, preparation method and application thereof in preparation of phenolic compounds
CN109796305B (en) Method for preparing cyclohexanol by adopting composite catalyst
CN109251125B (en) Method for preparing cyclohexanol by oxidizing cyclohexane
CN112007676B (en) Super-hydrophobic high-dispersion supported tungsten carbide catalyst and preparation method and application thereof
CN112169842B (en) Novel efficient supported Au/GO catalyst and preparation method and application thereof
CN116899605B (en) Preparation method of Co@NCNTs catalyst and application of Co@NCNTs catalyst in phenolic hydrogenation
CN115672358B (en) Preparation method and application of core-shell oxide catalyst for preparing ethylene by oxidative dehydrogenation of ethane
CN111167516B (en) Porous carbon supported monomolecular heteropoly acid catalyst and preparation method and application thereof
CN114920632B (en) Method for preparing p-methylbenzaldehyde by utilizing wood chips

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant