CN116651451A - Catalyst and process for alkynylation - Google Patents

Catalyst and process for alkynylation Download PDF

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Publication number
CN116651451A
CN116651451A CN202310595396.8A CN202310595396A CN116651451A CN 116651451 A CN116651451 A CN 116651451A CN 202310595396 A CN202310595396 A CN 202310595396A CN 116651451 A CN116651451 A CN 116651451A
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catalyst
reaction
stirring
hours
acetylene
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Inventor
马啸
宦关生
马慧娟
俞晓江
于明
张磊
樊国涛
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Shandong Nhu Pharmaceutical Co ltd
Zhejiang NHU Co Ltd
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Shandong Nhu Pharmaceutical Co ltd
Zhejiang NHU Co Ltd
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Abstract

The present invention relates to a catalyst for an alkynylation reaction and to a process for alkynylation. For the catalyst, a modifier is included, as well as a metal oxide system that is a first metal element doped support oxide, the modifier being present in at least a portion of the surface area of the metal oxide system. For the alkynylation process, a step comprising reacting a carbonyl-containing compound with a terminal alkynyl-containing compound in the presence of the catalyst is used.

Description

Catalyst and process for alkynylation
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a catalyst for an alkynylation reaction of a carbonyl compound, and further provides an alkynylation method of the carbonyl compound using the catalyst.
Background
Alkynol is an important fine chemical product, and is mainly used for producing perfumes such as VE main intermediates, DV chrysanthemic acid (chrysanthemic acid intermediates), vitamin A, vitamin K1, carotenoid intermediates, synthetic rubber monomers, linalool and the like.
For the preparation of alkynols, methods have been provided, for example, the preparation of the format reagent containing an alkynyl group in cited document 1 and cited document 2, and the reaction with a carbonyl compound to give alkynols; the elimination reaction of halogen-containing unsaturated alcohols is used in reference 3 to remove hydrogen halide to obtain alkynols.
Further, in industrial production of alkynols, generally, ketone or aldehyde is used as a raw material, acetylene gas is dissolved in liquid ammonia, and the acetylene gas is synthesized with a substrate under the action of an alkaline catalyst, and the reaction formula is as follows:
wherein R1 and R2 are hydrogen or hydrocarbyl.
Reference 4 discloses reacting a carbonyl compound with acetylene in the presence of ammonia and an alkali metal hydroxide, and in the examples, the highest conversion is about 95% and the selectivity is about 99%.
Reference 5 discloses that ketone and acetylene are used as raw materials, potassium isobutanol is used as a catalyst, and the raw materials of ketone, ethyl acetate and potassium isobutanol continuously enter a reactor, and in the patent, only potassium isobutanol is used as the catalyst, ammonia is not required, but the catalyst is high in cost and difficult to recycle.
In cited document 6, it is disclosed that ketone and acetylene are used as raw materials, flaky potassium hydroxide is used as a catalyst, ether and water are used as solvents, and a nonionic surfactant is added, water is removed under the azeotropic condition, KOH is suspended in an organic phase, and after the temperature is reduced to below 20 ℃, ketone and acetylene are introduced under normal pressure to react. However, the method has the problems of limiting the reaction rate due to small acetylene solubility and difficulty in separating products.
Reference 7 discloses a novel process for synthesizing alkynol from acetylene and ketone compounds, which comprises the steps of mixing acetylene and solvent ammonia gas, compressing, adding ketone compounds and potassium hydroxide catalyst, completing alkynylation reaction in a reactor, adding ammonium chloride to terminate the reaction, performing pressurized degassing, normal pressure degassing, scraping plate evaporation and ketone removal to obtain a crude alkynol product, and performing membrane separation to remove water to obtain an anhydrous alkynol product. However, the method uses strong alkali potassium hydroxide as a catalyst, and various side reactions can occur while the main reaction is carried out; the reaction is also terminated by the addition of ammonium chloride, resulting in the production of waste salts.
Reference 8 discloses an ethynylation method, wherein N, N-dimethylformamide is used as a solvent, inorganic cyanide such as sodium cyanide, potassium cyanide and the like is used as a side reaction inhibitor, and saturated or unsaturated ketone or aldehyde compounds are subjected to ethynylation reaction in the presence of catalyst alkoxide or amino salt to obtain corresponding alkynol compounds. However, the method needs to be extracted for multiple times, the required water amount is 30-200% of the solvent mass, the operation is complicated, more waste water is generated, and the use of highly toxic cyanide brings safety risks to operators.
Although, as mentioned above, the prior art has explored to some extent various synthetic methods for alkynols. There is still room for further improvement.
Citation literature:
citation 1: CN112375091A
Citation 2: CN104744211A
Citation 3: CN107032956A
Citation 4: CN1675152A
Citation 5: CN1769254A
Citation 6: CN102476978A
Citation 7: CN106117010A
Citation 8: CN110467519B
Disclosure of Invention
Problems to be solved by the invention
As previously mentioned, it is now common for commercial large-scale production of alkynols to catalyze the alkynylation of aldehydes or ketones under basic conditions using a catalyst, which reaction is essentially a nucleophilic addition reaction: the alkyne terminal C-H bond breaks under base catalysis to form an alkyne carbanion, which attacks, as a nucleophile, a positively charged carbon atom in the carbonyl group (the carbonyl group is a polar functional group, the electronegativity of the oxygen atom in the carbonyl group is greater than that of the carbon atom, and therefore the oxygen is negatively charged, and the carbon is positively charged). However, under alkaline conditions, in addition to the main reaction, there are also various side reactions, such as further reaction of alkynols to form alkynediols, which decompose by heat. In addition, aldol condensation reaction itself under alkaline conditions as a raw material aldehyde or ketone is also liable to produce by-products, and occurrence of these side reactions all results in lower reaction yields.
In addition, in the current industrial practice, the basic catalyst used in large amounts thereof is hardly recovered and thus cannot be reused, which not only results in high production costs but also easily causes environmental problems. In addition, in order to use ammonia as a solvent, ammonia is liquefied first, a very low temperature is required, and the refrigeration energy consumption is considerable, which has become a great burden on the energy consumption.
Accordingly, in view of the above-described problems in the art of industrial production of alkynols, the present invention primarily provides a reaction catalyst suitable for preparing alkynol compounds from carbonyl-containing compounds and alkynyl-containing compounds, which is obtained by modifying a metal-doped support oxide with a nitrogen-containing heterocyclic compound. The catalyst of the present invention can inhibit side reactions and can provide catalyst recyclability.
Furthermore, the invention also provides a preparation method of the alkynol by using the catalyst, which not only has improved yield, but also can reduce or even avoid the use of solvents, thus the method belongs to an efficient and environment-friendly ethynylation method and is beneficial to the industrialized mass production of the alkynol and downstream products thereof.
Solution for solving the problem
Through long-term research by the inventor, the technical problems can be solved through implementation of the following technical scheme:
[1] The present invention provides, first of all, a catalyst for the preparation of alkynols via reaction of carbonyl-containing compounds with terminal alkynyl-containing compounds, wherein,
the catalyst comprises a modifier and a metal oxide system, wherein the metal oxide system is a carrier oxide doped with a first metal element,
wherein,,
the modifier comprises a nitrogen-containing heterocyclic compound,
the first metal element includes one or more of Pd, ru, pt, nb, bi, cu and Co, preferably, a combination of two or more elements,
and, the modifier is present in at least a portion of the surface region of the metal oxide system.
[2] The catalyst according to [1], wherein the carbonyl-containing compound has a molecular formula represented by the following formula (I):
wherein R is 1 、R 2 Each occurrence of which is the same or different and is each independently hydrogen or a monovalent organic group, or R 1 And R is 2 May be linked to form a ring, provided that R 1 、R 2 Not both hydrogen.
[3] The catalyst according to [1] or [2], wherein the terminal alkynyl-containing compound has the formula (II) below,
wherein R is 3 Is hydrogen or a monovalent organic group.
[4] The catalyst according to any one of [1] to [3], wherein the nitrogen-containing heterocyclic compound is selected from one or more of pyridines, imidazoles, pyrazoles, quinolines, oxazolines.
[5] The catalyst according to any one of [1] to [4], wherein the content of the first metal element in the metal oxide system is 0.1 to 10 mass% based on the mass of the doped carrier oxide.
[6] The catalyst according to any one of [1] to [5], wherein in the catalyst, the molar ratio of the nitrogen-containing heterocyclic compound to the first metal element is 10 to 20:1.
[7] Further, the invention also provides a preparation method of alkynol, wherein the method comprises the following steps:
a step of reacting a carbonyl-containing compound with an alkynyl-containing compound in the presence of the catalyst according to any one of [1] to [6] above.
[8] The method according to [7], wherein the reaction is carried out with or without using a solvent.
[9] The method according to [7] or [8], wherein the temperature of the reaction is 70℃or lower and the time of the reaction is 6 hours or less.
[10] The method according to any one of [7] to [9], wherein the catalyst is a freshly prepared catalyst or a reused catalyst.
ADVANTAGEOUS EFFECTS OF INVENTION
In the present invention, through implementation of the above technical solution, it has been found that the present invention can obtain the following technical effects:
(1) The alkynylation method and the catalyst thereof for carbonyl compounds provided by the invention not only inhibit alkynol from further generating alkynediol, but also eliminate the heating decomposition of alkynol products and the self-condensation reaction of substrate aldehyde or ketone, thereby effectively improving the product yield and the raw material utilization rate.
(2) The alkynylation method provided by the invention has a simple reaction system, can be successfully carried out even under the condition of not using a solvent, therefore, extraction treatment is not needed after the reaction is finished to extract products, salt quenching reaction is not needed to be added, the catalyst is easy to recycle, waste water and waste salt are not generated, the environment is protected, and the post-treatment operation is greatly simplified.
(3) The heterogeneous metal doped catalyst used in the invention is easy to recycle, and the catalyst has stable performance, realizes the recycling of the catalyst, effectively reduces the production cost, and is beneficial to improving the competitiveness of alkynol and downstream products thereof.
Drawings
FIG. 1 is an SEM photograph of the morphology of a catalyst of example 17;
FIG. 2 is a graph and results of the gas phase detection of the ethynylation reaction solution of example 24;
FIG. 3 is a graph showing the detection result of the ethynylation reaction liquid in example 43.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In the present specification, the use of "optional" or "optional" means that some substances, components, steps of execution, conditions of application, and the like may or may not be used, and the manner of use is not limited.
In the present specification, the use of "unsaturated structure" refers to a structure formed by carbon-carbon double bonds, unless otherwise specifically indicated.
In the present specification, "hydrocarbon group" is used to denote an organic structure formed of two elements of carbon and hydrogen, and may be an aromatic or non-aromatic group.
In the present specification, the use of "halogen" means fluorine, chlorine, bromine or iodine. Preferred are fluorine, chlorine or bromine, and more preferred are bromine and chlorine.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
Reference throughout this specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
The invention mainly provides a catalyst which is suitable for preparing alkynol by the alkynylation reaction of carbonyl compounds, and simultaneously, the invention also provides a synthetic method for preparing alkynol by using the catalyst.
Further, the present invention is mainly based on the following findings:
the catalyst of the invention comprises: a metal oxide system obtained by doping a first metal element and a modifier present in at least a partial region of the surface of the metal oxide system.
It has been found that the basicity of the support oxide after doping with the first metal is significantly enhanced, promoting cleavage of the c—h bond in the alkyne to form a carbanion, acting as a nucleophile to attack a carbonyl-containing substrate (such as an aldehyde or ketone), significantly increasing the rate and conversion of the reaction. The substrate (aldehyde or ketone) is adsorbed on the active site on the surface of the catalyst, and the alkynol product is rapidly separated after the reaction is finished, so that the reaction selectivity is improved.
The modifier on the catalyst also plays a role in modifying the catalyst, and the mechanism of the modified catalyst is not completely clear, but presumably, the modifier combined with the surface of the metal oxide system has larger steric hindrance, but does not influence the catalytic alkalinity of the catalyst because of the electronic property of the modifier, and the alkynol serving as a product cannot be continuously adsorbed on the surface of the catalyst to continuously carry out nucleophilic addition reaction, so that the generation of alkynediol byproducts is avoided, and the reaction yield is improved. The nitrogen atom in the nitrogen heterocycle has an electron donating property and can be chelated with metal, so that a stable metal complex is formed; in addition, the nitrogen atoms are easy to generate electron transfer, so that the catalyst can be recycled.
< first aspect >
In a first aspect of the invention, a catalyst suitable for the alkynylation of carbonyl-containing compounds with terminal alkynyl-containing compounds is provided.
The catalyst of the invention is a heterogeneous catalyst for the alkynylation reaction, the catalyst comprising a metal oxide system and a modifier present in at least a partial region of the surface of the metal oxide system.
(carbonyl-containing Compound)
The carbonyl-containing compound of the present invention is not particularly limited in principle as long as it has usefulness for producing alkynols.
In some specific embodiments of the present invention, there may be one or more carbonyl groups for the carbonyl-containing compounds of the present invention. Such carbonyl groups may be present in the form of aldehyde groups or ketone groups. In the case of a carbonyl group, the corresponding alkynol can be obtained by reaction with an alkynyl group; in the case of having a plurality of carbonyl groups, a corresponding compound having a plurality of alkynol groups can be obtained as well, or, depending on the actual need, a part of carbonyl groups not requiring the alkynylation reaction can be protected, thereby the alkynylation reaction is carried out only at a specific site, and the manner of the protection is not particularly limited and can be carried out by a conventional manner known in the art.
In some embodiments of the invention, the carbonyl-containing compound has a structure or formula as shown in formula (I):
wherein R is 1 、R 2 Each occurrence of which is the same or different and is each independently hydrogen or a monovalent organic group, or R 1 And R is 2 May be linked to form a ring, provided that R 1 、R 2 Not both hydrogen.
The monovalent organic group is not particularly limited in principle as long as it does not affect the progress of the alkynylation reaction. In some specific embodiments, for monovalent organic groups, they may be selected from hydrocarbon groups having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, or 3 to 20 carbon atoms.
For these monovalent groups, they may be saturated hydrocarbon groups or hydrocarbon groups having one or more unsaturated structures; in other specific embodiments, the hydrocarbyl structures may have any linear, branched, or cyclic structure, which may also have any one or more saturated structures (e.g., aromatic structures, etc.). In some preferred embodiments, it may be a straight chain, branched or having (partially) cyclic structural group formed of 1 to 15 or 2 to 10 carbon atoms, and having 1 or two unsaturated structures.
Further, as the monovalent group, the above-mentioned hydrocarbon group may further have an optional substituent, and these substituents may be selected from the group consisting of a halogen group, a nitrogen-containing group, a sulfur-containing group, an oxygen-containing group (e.g., an alkoxy group), and the like, without limitation. In addition, for the above hydrocarbon groups, every two carbon atoms in the hydrocarbon chain may be interrupted by atoms of silicon, oxygen, sulfur or groups centered thereon.
Further, in some preferred embodiments of the present invention, the compound of formula (I) may be selected from any one of the group including, but not limited to, formaldehyde, acetone, butanone, 6-methyl-5-hepten-2-one, 6-methyl-5-octen-2-one, 6-methyl-2-heptanone, geranylacetone, tetrahydrogeranylacetone, plant ketones, and furfural.
And, by the invention, the following alkynylation reaction will be described, with the corresponding structure formed being (for example acetylene): propargyl alcohol, 2-methyl-3-butyn-2-ol, 3-methyl-pentyn-3-ol, dehydrolinalool, dehydroethyl linalool, dihydrodehydrolinalool, furfuryl ethynyl alcohol, dehydronerolidol, tetrahydrodehydronerolidol, dehydroisophytol, and their structural formulas are respectively:
(terminal alkynyl-containing Compound)
The terminal alkynyl-containing compounds of the present invention are primarily useful for providing nucleophilic attack groups for alkynylation reactions. Therefore, the present invention is not particularly limited as long as it is a compound capable of realizing an alkynylation reaction.
In some specific embodiments, wherein the terminal alkynyl-containing compound has the formula (II) below,
wherein R is 3 Is hydrogen or a monovalent organic group. For monovalent organic groups, it is in principle possible to have the same selection ranges as described above for monovalent organic groups. From the viewpoint of synthesis economy and downstream utilization of alkynol products, R 3 Preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, more preferably R 3 Is a hydrogen atom.
For the terminal alkynyl-containing compound of the present invention, the purity in the below-described alkynylation reaction, preferably, it may have a purity of 99% or more in order to reduce occurrence of side reactions.
(Metal oxide System)
For the metal oxide systems of the present invention, it is primarily intended to provide catalytic basicity to enhance the nucleophilic reactivity of terminal alkynyl-containing compounds.
Specifically, the metal oxide system of the present invention can be obtained by doping a carrier oxide with a first metal element.
For the first metal element, in some specific embodiments of the present invention, one or more of Pd, ru, pt, nb, bi, cu, co may be included. Preferably, the first metal element includes a combination of two or more of the above elements from the viewpoint of improving substrate conversion and selectivity.
There is in principle no particular limitation on the support oxide as long as it provides sufficient basicity and reaction sites. In some specific embodiments, the support oxide may be an oxide of a metal (hereinafter referred to as a "second metal"). The second metal may contain one of a transition metal and a main group metal or a mixed metal thereof. In some specific embodiments of the present invention, the second metal may include the same metal element as the first metal element, or the second metal may not include the same metal element as the first metal element. And, when the second metal includes the same metal element as the first metal element, the same metal element has a higher surface concentration than an inner concentration in the metal oxide system.
Further, the carrier oxides useful in the present invention may be selected from CeO in terms of efficiency, selectivity and yield in carrying out the alkynylation reaction 2 、BaCeO 3 、CaFeO 3 、LaCoO 3 、LaNiO 3 、LaFeO 3 、γ-Al 2 O 3 One or more of the following.
The morphology of the support oxide may be in the form of particles having a porous surface, and such support oxide may be obtained by homemade or commercially available.
In addition, by a carrier oxide doped with a first metal element is meant that at least part of the first metal element has entered the lattice structure in the carrier oxide.
(modifier)
The main function of the modifier of the present invention is to provide surface modification to the metal oxide system without affecting the catalytic basicity, to provide an effective steric effect.
For the modifier of the present invention, a nitrogen-containing heterocyclic compound in which the nitrogen atom provides an effective electronic effect, and the cyclic structure can provide an effective steric effect may be included.
The nitrogen-containing heterocyclic compound of the present invention is not particularly limited as long as one nitrogen atom exists in a saturated or unsaturated ring structure, and preferably, the nitrogen-containing heterocyclic compound may be selected from one or more of pyridines, imidazoles, pyrazoles, quinolines, oxazolines.
Further, the nitrogen-containing ligand may preferably be selected from one or more of the following nitrogen-containing heterocyclic compounds of L1 to L10:
the compound having the above structure is not limited, and other substituent groups may be present in the cyclic structure, and for these groups, alkyl groups, cycloalkyl groups, aryl groups, and the like having 1 to 30 carbon atoms or 2 to 20 carbon atoms are preferable.
Further, the bonding method of the modifier to the metal oxide system is not particularly limited, and the modifier may be applied to at least a part of the surface area of the metal oxide system by dipping or coating.
(catalyst)
As described above, the catalyst of the present invention comprises the metal oxide system described above, and a modifier present in at least a portion of the surface of the metal oxide system.
For the metal oxide system obtained by doping the first metal element, the content of the first metal element may be 0.1 to 10 mass%, preferably 0.5 to 9 mass%, more preferably 1 to 8 mass%, for example 1.5 mass%, 2 mass%, 2.5 mass%, 3 mass%, 3.5 mass%, 4 mass%, 4.5 mass%, 5 mass%, 5.5 mass%, 6 mass%, 6.5 mass%, 7 mass%, 7.5 mass%, etc., of the mass of the doped carrier oxide.
Further, for the amount of modifier used, the molar ratio of the nitrogen-containing heterocyclic compound to the first metal element in the catalyst is 10 to 20:1, preferably 12 to 18:1, more preferably 13 to 16:1.
< second aspect >
In a second aspect of the present invention, there is provided a method for preparing the catalyst in the first aspect, the method mainly comprising:
i. doping a first metal element;
and ii, loading the modifier.
(step i)
For doping the first metal element into the carrier oxide, the first metal element is at least partially inserted into the lattice structure of the carrier oxide to improve the overall alkalinity.
In some specific embodiments of the invention, step i may be performed by calcination of the first metal source and the support oxide.
For the first metal source, it may be various acid salts of the first metal or their hydrates, such as one or more of nitrate, hydrochloride, sulfate, acetate, citrate, formate, ammonium salts, and their hydrates. Preferably, these first metal sources are water-soluble metal salts from the viewpoint of convenience of operation.
In some embodiments, the first metal source, the support oxide and the solvent (water or organic solvent, etc.) may be mixed to form a mixed system, and preferably, the mixed system may be mixed at 100 to 160 ℃ for 2 to 6 hours, so that the first metal source is adsorbed on the surface of the support oxide, and then taken out and baked.
The conditions for firing are not particularly limited in principle, and for example, firing may be performed under atmospheric conditions at 400 to 600 ℃ to obtain a catalyst precursor doped with the first metal element.
(step ii)
The mode of loading the modifier is not particularly limited in principle. For example, in some embodiments, the catalyst precursor may be impregnated with a solution in which the modifier is dissolved or dispersed, or coated (e.g., sprayed) onto the surface of the catalyst precursor with a solution in which the modifier is dissolved or dispersed to obtain the catalyst of the present invention. In some preferred embodiments, the catalyst precursor may be impregnated in a solution in which the modifier is dispersed or dissolved using an impregnation method, and preferably, may be mixed at 100 to 160 ℃ for 2 to 6 hours.
(other auxiliary means)
The other auxiliary preparation methods other than the above two steps are not particularly limited, and for example, the method of washing, stirring, drying, and the like may be appropriately performed with reference to various known methods in the art. The organic solvents that may be used in the above steps are not particularly limited, and examples thereof include alcohol solvents and aromatic solvents.
< third aspect >
In a third aspect the invention relates to a process for carrying out an alkynylation reaction using the catalyst of the first aspect of the invention.
Specifically, the alkynylation reaction method of the present invention comprises a step of reacting a carbonyl-containing compound with a terminal alkynyl-containing compound in the presence of a catalyst.
In some specific embodiments, the alkynylation reaction of the present invention is carried out with or without the use of a solvent. Therefore, it is more economical and environmentally friendly than the conventional industrial process using liquid ammonia as an essential solvent in the prior art.
In addition, the solvents allowed in the present invention are not particularly limited as long as they are inert in principle to the alkynylation reaction, and in some specific embodiments, these solvents may include alcohol solvents, aromatic solvents (e.g., toluene, xylene), ether solvents, and the like.
Further, the temperature of the alkynylation reaction may be generally 70℃or lower, preferably 30 to 60℃and more preferably 40 to 55℃and the time of the alkynylation reaction may be 6 hours or less, for example, 2 to 4 hours.
In some preferred embodiments, the mass concentration of the catalyst in the reaction system is controlled to be 9% or less, preferably 2 to 7%.
In addition, considering that some of the terminal alkynyl-containing compounds are in a gaseous state, the reaction may be carried out under a pressurized state, for example, the alkynylation reaction may be carried out under a condition of 0.15 to 0.25 MPa.
In the present invention, the reaction is terminated without using a catalytic inhibitor such as ammonium chloride, and the final product can be directly isolated after the completion of the alkynylation reaction without using a solvent. In this case, the final product is isolated and a solid catalyst is obtained.
Thus, for the alkynylation reaction of the present invention, the catalyst used therein may be either fresh catalyst (unused) prepared via the preparation process of the second aspect of the present invention or regenerated catalyst recovered from the completed alkynylation reaction.
For the catalyst recovery mode, in some specific embodiments it may be:
when the conversion of the reactant (carbonyl-containing compound) is detected to be below a specified level, such as 90% or 80%, then catalyst deactivation is specified. After the catalyst is deactivated, the catalyst is taken out from the reaction system, washed and placed in a vacuum drying oven with the temperature of more than 100 ℃ for activation treatment for 4 to 6 hours, and the activity can be recovered.
Further, in the case of using the catalyst of the present invention for the alkynylation reaction of the present invention, the conversion rate of the carbonyl-containing compound may be preferably 88% or more, preferably 90% or more, more preferably 95% or more, and the selectivity may be 85% or more, preferably 90% or more, more preferably 92% or more.
Examples
Embodiments of the present invention will be described in detail below with reference to examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
1.25g Pd (NO) was added to 30mL deionized water 3 ) 2 ·2H 2 1.62g of Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 4 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. 11.74g of ligand 4,4' -bipyridine (L1, MW: 156.18) was dispersed in 30mL deionized water and thoroughly stirred Mixing, adding precursor, heating to 120deg.C, stirring at 400r/min for 4 hr, removing water by rotary evaporation under reduced pressure to obtain solid, placing in vacuum drying oven at 100deg.C, and drying to constant weight to obtain catalyst 5.0% Pd-7.0% Bi/BaCeO 3 -L1。
Example 2
1.25g Pd (NO) was added to 30mL deionized water 3 ) 2 ·2H 2 O, 1.16g Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 80 ℃, continuously stirring for 6 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 19.03g of ligand L10 (MW: 253.11) in 50mL of deionized water, stirring and mixing thoroughly, adding precursor, heating to 120deg.C, stirring at 400r/min for 4 hr, removing water by rotary evaporation under reduced pressure to obtain solid, placing in a vacuum drying oven at 100deg.C, and drying to constant weight to obtain catalyst 5.0% Pd-5.0% Bi/BaCeO 3 -L10。
Example 3
In 30mL of deionized water, 0.75g of Pd (NO) 3 ) 2 ·2H 2 O, 1.62g Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 4 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 600 ℃ for 4 hours, cooling, and taking out to obtain the precursor. Dispersing 11.42g of ligand L10 in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 4 hours, decompressing and steaming to remove water to obtain a solid, placing in a 100 ℃ vacuum drying oven, and drying to constant weight to obtain the catalyst 3.0% Pd-7.0% Bi/BaCeO 3 -L10。
Example 4
1.17g of PdCl was added to 30mL of deionized water 2 Stirring for 400r/min, and adding 1.43g of Nb after complete dissolution 2 O 5 10.0g of CaFeO 3 Heating the carrier to 100 ℃, continuously stirring for 4 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 20.55g of ligand 2,2' -bipyridine (L2, MW: 156.18) in 50mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 4 hours, decompressing and steaming to remove water, obtaining a solid, placing in a vacuum drying oven at 100 ℃, and drying to constant weight to obtain the catalyst 7.0% Pd-5.0% Nb/CaFeO 3 -L2。
Example 5
1.29g of RuCl was added to 30mL of deionized water 3 ·3H 2 O, 3.52g of Ce (NH) 4 ) 2 (NO 3 ) 6 Stirring for 400r/min, and adding 10.0g LaCoO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 4 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 600 ℃ for 4 hours, cooling, and taking out to obtain the precursor. Dispersing 8.38g of ligand 4-aminopyridine (L3, MW: 94.11) in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 4 hours, performing reduced pressure rotary evaporation to remove water to obtain a solid, placing in a vacuum drying oven at 100 ℃, and drying to constant weight to obtain a catalyst of 5.0% Ru-9.0% Ce/LaCoO 3 -L3。
Example 6
1.29g of RuCl was added to 30mL of deionized water 3 ·3H 2 O, 1.62g Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g LaFeO after complete dissolution 3 Heating the carrier to 100deg.C, stirring for 4 hr, removing water by rotary evaporation under reduced pressure to obtain solid, and vacuum drying in a vacuum drying oven at 100deg.CDrying to constant weight; taking out, placing in a muffle furnace, calcining at 600 ℃ for 5 hours, cooling, and taking out to obtain the precursor. Dispersing 8.38g of ligand 4-aminopyridine (L3, MW: 94.11) in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 4 hours, performing reduced pressure rotary evaporation to remove water to obtain a solid, placing in a vacuum drying oven at 100 ℃, and drying to constant weight to obtain a catalyst of 5.0% Ru-7.0% Bi/LaFeO 3 -L3。
Example 7
In 50mL of deionized water, 0.75g of Pd (NO 3 ) 2 ·2H 2 O, 1.95g Ce (NH) 4 ) 2 (NO 3 ) 6 Stirring for 400r/min, and adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 5 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 600 ℃ for 5 hours, cooling, and taking out to obtain the precursor. Dispersing 8.81g of ligand 4,4' -bipyridine (L1) in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 5 hours, performing reduced pressure rotary evaporation to remove water to obtain a solid, placing in a 100 ℃ vacuum drying oven, and drying to constant weight to obtain the catalyst 3.0% Pd-5.0% Ce/BaCeO 3 -L1。
Example 8
Into 50mL of deionized water, 0.86g of PtCl was added 4 Cu (OAc) 3.14g 2 ·H 2 O, stirring for 400r/min, adding 10.0g of LaNiO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 4 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 600 ℃ for 4 hours, cooling, and taking out to obtain the precursor. Dispersing 4.26g ligand 3-aminopyrazole (L4, MW: 83.09) in 30mL deionized water, stirring thoroughly, adding precursor, heating to 120deg.C, stirring at 400r/min for 4 hr, steaming under reduced pressure to remove water to obtain solid, and vacuum-evaporating at 100deg.CDrying in a drying oven to constant weight to obtain catalyst 5.0% Pt-10.0% Cu/LaNiO 3 -L4。
Example 9
Into 50mL of deionized water, 0.50g of PdCl was added 2 Co (OAc) 2.96g 2 ·4H 2 O, stirring for 400r/min, adding 10.0g LaFeO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 4 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 600 ℃ for 5 hours, cooling, and taking out to obtain the precursor. Dispersing 4.17g of ligand 4-methylpyrazole (L5, MW: 82.11) in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at constant temperature of 400r/min for 4 hours, performing reduced pressure rotary evaporation to remove water to obtain a solid, placing in a vacuum drying oven at 100 ℃, and drying to constant weight to obtain the catalyst 3.0% Pd-7.0% Co/LaFeO 3 -L5。
Example 10
Into 50mL of deionized water, 0.86g of PtCl was added 4 CuSO 3.54g 4 ·5H 2 O, stirring for 400r/min, adding 10.0g CeO after complete dissolution 2 Heating the carrier to 120 ℃, continuously stirring for 6 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 4.43g of ligand 5-aminoquinoline (L6, MW: 144.17) in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, performing reduced pressure rotary evaporation to remove water to obtain a solid, placing in a vacuum drying oven at 100 ℃, and drying to constant weight to obtain a catalyst of 5.0% Pt-9.0% Cu/CeO 2 -L6。
Example 11
1.29g of RuCl was added to 50mL of deionized water 3 ·3H 2 O, 1.62g Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding after complete dissolution10.0g of gamma-Al 2 O 3 Heating the carrier to 120 ℃, continuously stirring for 6 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 22.82g of ligand 2,2' -biquinoline (L7, MW: 256.3) in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing in a vacuum drying oven at 100 ℃, and drying to constant weight to obtain a catalyst of 5.0% Ru-7.0% Bi/gamma-Al 2 O 3 -L7。
Example 12
Into 50mL of deionized water, 0.86g of PtCl was added 4 1.62g of Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 6 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 4.67g of ligand 4, 4-dimethyl oxazoline (L8, mw: 101.15) in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing in a vacuum drying box at 100 ℃, and drying to constant weight to obtain a catalyst of 5.0% Pt-7.0% Bi/BaCeO 3 -L8。
Example 13
Into 50mL of deionized water, 0.50g of PdCl was added 2 1.96g of Ce (NH) 4 ) 2 (NO 3 ) 6 Stirring for 400r/min, and adding 10.0g LaFeO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 4 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 12.85g of ligand L9 in 50mL of deionized water Adding a precursor into water, fully stirring and mixing, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight to obtain the catalyst 3.0% Pd-5.0% Ce/LaFeO 3 -L9。
Example 14
In 50mL of deionized water, 0.25g of Pd (NO) 3 ) 2 ·2H 2 O, 1.62g Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 100 ℃, continuously stirring for 5 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 4.76g of ligand L10 in 30mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing in a 100 ℃ vacuum drying oven, and drying to constant weight to obtain the catalyst 1.0% Pd-7.0% Bi/LaFeO 3 -L10。
Example 15
Into 50mL of deionized water, 0.83g of PdCl was added 2 2.74g of Ce (NH) 4 ) 2 (NO 3 ) 6 Stirring for 400r/min, and adding 10.0g LaCoO after complete dissolution 3 Heating the carrier to 160 ℃, continuously stirring for 5 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 8 hours, cooling, and taking out to obtain the precursor. Dispersing 19.03g of ligand L10 in 50mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing in a 100 ℃ vacuum drying oven, and drying to constant weight to obtain the catalyst 5.0% Pd-7.0% Ce/LaCoO 3 -L10。
Example 16
In 50mL of deionized water, 0.75g of Pd (NO 3 ) 2 ·2H 2 O, 1.62g Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 160 ℃, continuously stirring for 5 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 12.85g of ligand L10 in 50mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing in a 100 ℃ vacuum drying oven, and drying to constant weight to obtain the catalyst 3.0% Pd-7.0% Bi/BaCeO 3 -L10。
Example 17
1.25g Pd (NO) was added to 30mL deionized water 3 ) 2 ·2H 2 O, 1.62g Bi (NO) 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 160 ℃, continuously stirring for 5 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 11.89g of ligand L10 in 50mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing in a 100 ℃ vacuum drying oven, and drying to constant weight to obtain the catalyst 5.0% Pd-7.0% Bi/BaCeO 3 -L10. An electron microscope scanning photograph of the catalyst morphology is shown in figure 1.
Example 18
Into 30mL of deionized water, 0.75g of Bi (NO 3 ) 2 ·5H 2 O, 3.52g of Ce (NH) 4 ) 2 (NO 3 ) 6 Stirring for 400r/min, and adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 140 ℃, continuously stirring for 5 hours, and reducingRemoving water by rotary pressure evaporation to obtain solid, and placing in a vacuum drying oven at 100 ℃ to dry to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 16.95g of ligand L10 in 50mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing in a 100 ℃ vacuum drying oven, and drying to constant weight to obtain the catalyst 7.0% Bi-9.0% Ce/BaCeO 3 -L10。
Example 19
1.62g of Bi (NO) was added to 30mL of deionized water 3 ) 2 ·5H 2 O, 3.63g of CoCl 2 ·6H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 140 ℃, continuously stirring for 5 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 16.95g of ligand L10 in 50mL of deionized water, fully stirring and mixing, adding a precursor, heating to 120 ℃, stirring at a constant temperature of 400r/min for 6 hours, decompressing and steaming to remove water to obtain a solid, placing in a 100 ℃ vacuum drying oven, and drying to constant weight to obtain the catalyst 7.0% Bi-9.0% Co/BaCeO 3 -L10。
Example 20
1.26g Pd (NO) was added to 30mL deionized water 3 ) 2 ·2H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 140 ℃, continuously stirring for 5 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the precursor. Dispersing 23.79g of ligand L10 in 50mL of deionized water, stirring and mixing thoroughly, adding precursor, heating to 120deg.C, stirring at 400r/min for 6 hr under constant temperature, removing water by rotary evaporation under reduced pressure to obtain solid, placing in a vacuum drying oven at 100deg.C, and drying to constant temperatureHeavy weight to obtain catalyst 5.0% Pd/BaCeO 3 -L10。
Example 21
Into 30mL of deionized water, 2.09g of Bi (NO 3 ) 2 ·5H 2 O, stirring for 400r/min, adding 10.0g of BaCeO after complete dissolution 3 Heating the carrier to 140 ℃, continuously stirring for 5 hours, decompressing, steaming to remove water, obtaining solid, placing the solid in a vacuum drying oven at 100 ℃, and drying to constant weight; taking out, placing in a muffle furnace, calcining at 500 ℃ for 6 hours, cooling, and taking out to obtain the catalyst 9.0% Bi/BaCeO 3 。
Example 22
Into an autoclave, 50.0g of acetone, 2.5g of catalyst 5.0% Pd-7.0% Bi/BaCeO were added 3 L1 (catalyst mass concentration 5.0%), 3 times with nitrogen and 3 times with acetylene, stirring, setting temperature to 40 ℃, reacting at constant temperature, and maintaining acetylene pressure at 0.20MPa. The reaction is carried out for 4.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the acetone conversion rate is 98.61 percent, and the selectivity of 2-methyl-3-butyn-2-ol is 95.53 percent.
The reaction mixture was distilled under reduced pressure to recover unreacted raw materials, 68.11g of a crude 2-methyl-3-butyn-2-ol was obtained, and the yield was 94.08%.
Example 23
Into an autoclave, 50.0g of acetone, 1.5g of catalyst 5.0% Pd-5.0% Bi/BaCeO were added 3 L10 (catalyst mass concentration 3.0%), 3 times with nitrogen and 3 times with acetylene, stirring, setting temperature to 50deg.C, constant temperature reacting, and maintaining acetylene pressure at 0.20MPa. The reaction is carried out for 4.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the acetone conversion rate is 98.82 percent, and the selectivity of the 2-methyl-3-butyn-2-ol is 96.71 percent.
The reaction solution was distilled under reduced pressure, and unreacted raw materials were recovered to obtain 69.09g of a crude 2-methyl-3-butyn-2-ol, and a yield of 95.43% was calculated.
Example 24
Into an autoclave, 50.0g of acetone, 3.5g of catalyst 5.0% Pd-7.0% Bi/BaCeO were added 3 L10 (catalyst mass concentration 7.0%), 50.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 4.5 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the acetone conversion rate is 99.62 percent, the selectivity of 2-methyl-3-butyn-2-ol is 99.53 percent, and the gas phase diagram of the reaction liquid is shown in figure 1.
The reaction mixture was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 71.71g of a crude 2-methyl-3-butyn-2-ol, whereby the yield was 99.05%.
Example 25
Into an autoclave, 50.0g of acetone, 2.5g of catalyst 5.0% Pd-5.0% Bi/BaCeO were added 3 L10 (catalyst mass concentration 5.0%), 50.0g deionized water, 3 times with nitrogen, 3 times with acetylene, start stirring, set temperature to 60 ℃, react at constant temperature, and maintain acetylene pressure 0.20MPa. The reaction is carried out for 4 hours, the pressure is released, the catalyst is filtered out from the pressed reaction liquid, the reaction liquid is detected by gas chromatography, the acetone conversion rate is 98.62 percent, and the selectivity of 2-methyl-3-butyn-2-ol is 93.28 percent.
The reaction mixture was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 66.27g of a crude 2-methyl-3-butyn-2-ol, whereby the yield was 91.53%.
Example 26
70.0g butanone, 3.51g catalyst 3.0% Pd-5.0% Bi/BaCeO were added to an autoclave 3 L10 (catalyst mass concentration 5.0%), 70.0g ethanol, 3 times with nitrogen, 3 times with acetylene, start stirring, set temperature to 60 ℃, react at constant temperature, and maintain acetylene pressure 0.20MPa. The reaction is carried out for 4 hours, the pressure is released, the catalyst is filtered out from the pressed reaction liquid, the reaction liquid is detected by gas chromatography, the butanone conversion rate is 98.73 percent, and the selectivity of the 3-methyl-pentyne-3-alcohol is 94.93 percent.
The reaction mixture was distilled under reduced pressure, and the solvent and unreacted starting materials were recovered to give 90.19g of a crude 3-methyl-pentyn-3-ol product, and the yield was 94.67%.
Example 27
Into an autoclave, 100.0g of 6-methyl-5-hepten-2-one, 7.0g of catalyst 7.0% Pd-5.0% Nb/CaFeO were added 3 L2 (catalyst mass concentration 7.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 50 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 3 hours, the pressure is released, the catalyst is filtered out from the pressed reaction liquid, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-hepten-2-one is 98.02%, and the selectivity of dehydrolinalool is 95.78%.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 112.86g of crude dehydrolinalool, and the yield was 93.56%.
Example 28
Into an autoclave, 100.0g of 6-methyl-5-octen-2-one, 5.0g of catalyst 5.0% Ru-9.0% Ce/LaCoO were added 3 L3 (catalyst mass concentration 5.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 50 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 4.5 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-octene-2-ketone is 98.12%, and the selectivity of dehydroethyl linalool is 97.48%.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 113.21g of a crude dehydroethyl linalool was obtained, and the yield was calculated to be 95.48%.
Example 29
Into an autoclave, 100.0g of 6-methyl-2-heptanone, 5.0g of catalyst 5.0% Ru-9.0% Ce/LaCoO were added 3 L3 (catalyst mass concentration 5.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. Reacting for 4 hours, decompressing, extruding the reaction liquid, filtering the catalyst, and making the reaction liquid pass through gas phase The conversion rate of 6-methyl-2-heptanone is 98.30 percent and the selectivity of the dihydro-dehydrolinalool is 97.63 percent according to chromatographic detection.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 115.26g of crude dihydrolinalool, which was calculated to yield 95.80%.
Example 30
In an autoclave, 100.0g of furfural, 5.0g of catalyst 5.0% Ru-7.0% Bi/LaFeO are added 3 L3 (catalyst mass concentration 5.0%), 100.0g toluene, 3 times with nitrogen and 3 times with acetylene, stirring, setting the temperature to 40 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 3.5 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of furfural is 98.44%, and the selectivity of furfuryl acetylene alcohol is 97.89%.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 123.61g of furfuryl acetylene alcohol crude product, and the yield was calculated to be 95.25%.
Example 31
In an autoclave, 100.0g of geranylacetone, 7.0g of catalyst 3.0% Pd-5.0% Ce/BaCeO were added 3 L1 (catalyst mass concentration 7.0%), 100.0g isopropyl alcohol, 3 times with nitrogen, 3 times with acetylene, start stirring, set temperature to 60 ℃, react at constant temperature, and maintain acetylene pressure 0.20MPa. The reaction is carried out for 4 hours, the pressure is released, the catalyst is filtered out from the pressed reaction liquid, the reaction liquid is detected by gas chromatography, the geranyl acetone conversion rate is 97.64%, and the selectivity of dehydronerolidol is 97.23%.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 107.58g of a crude dehydronerolidol product was obtained, and the yield was calculated to be 94.87%.
Example 32
Into an autoclave, 100.0g of tetrahydrogeranylacetone, 7.0g of catalyst 5.0% Pt-10.0% Cu/LaNiO were added 3 L4 (catalyst mass concentration 7.0%), 100.0g methanol, 3 times with nitrogen and 3 times with acetylene, stirring was started and the temperature was setThe temperature is 50 ℃ and the acetylene pressure is kept at 0.20MPa. After the reaction is carried out for 5.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the geranyl acetone conversion rate is 97.82%, and the selectivity of the tetrahydrodehydronerolidol is 96.05%.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 106.12g of a crude tetrahydrodehydronerolidol product was obtained, and the yield was calculated to be 93.81%.
Example 33
In an autoclave, 100.0g of plant ketone, 7.0g of catalyst 3.0% Pd-7.0% Co/LaFeO were added 3 L5 (catalyst mass concentration 7.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 5.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the plant ketone conversion rate is 97.42%, and the selectivity of dehydroisophytol is 97.35%.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 103.90g of crude dehydroisophytol, with a calculated yield of 94.72%.
Example 34
Into an autoclave, 100.0g of acetone, 7.0g of catalyst 5.0% Pt-9.0% Cu/CeO were added 2 L6 (catalyst mass concentration 7.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 5.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the acetone conversion rate is 98.48 percent, and the selectivity of 2-methyl-3-butyn-2-ol is 96.01 percent.
The reaction mixture was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 68.31g of a crude 2-methyl-3-butyn-2-ol, whereby 94.26% of yield was calculated.
Example 35
100.0g of butanone, 7.0g of catalyst 5.0% Ru-7.0% Bi/gamma-Al are added in an autoclave 2 O 3 L7 (catalyst mass concentration 7.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 40 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. After 5.0 hours of reaction, pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the butanone conversion rate is 96.57 percent, and the selectivity of 3-methyl-pentyne-3-alcohol is 95.62 percent.
The reaction mixture was distilled under reduced pressure, and the solvent and unreacted starting materials were recovered to give 125.43g of a crude 3-methyl-pentyn-3-ol product, and the yield was 92.16%.
Example 36
Into an autoclave, 100.0g of 6-methyl-5-hepten-2-one, 7.0g of catalyst 5.0% Pt-7.0% Bi/BaCeO were added 3 L8 (catalyst mass concentration 7.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 4.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-hepten-2-one is 97.69%, and the selectivity of dehydrolinalool is 96.73%.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 113.83g of crude dehydrolinalool, and the yield was 94.36%.
Example 37
Into an autoclave, 100.0g of 6-methyl-5-octen-2-one, 9.0g of catalyst 3.0% Pd-5.0% Ce/LaFeO were added 3 L9 (catalyst mass concentration 9.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 3.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-octene-2-ketone is 98.64%, and the selectivity of dehydroethyl linalool is 96.51%.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 112.71g of a crude dehydroethyl linalool was obtained, and the yield was calculated to be 95.06%.
Example 38
Into an autoclave, 100.0g of 6-methyl-2-heptanone, 7.0g of catalyst 1.0% Pd-7.0% Bi/LaFeO were added 3 L10 (catalyst mass concentration 7.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 50 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 4.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-octene-2-ketone is 95.31 percent, and the selectivity of the dihydro-dehydrolinalool is 96.34 percent.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 110.36g of crude dihydrolinalool, and the yield was 91.73%.
Example 39
In an autoclave, 100.0g of furfural, 5.0g of catalyst 5.0% Pd-7.0% Ce/LaCoO were added 3 L10 (catalyst mass concentration 5.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 50 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 6.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of furfural is 99.31%, and the selectivity of furfuryl acetylene alcohol is 98.29%.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 126.53g of furfuryl acetylene alcohol crude product, and the yield was calculated to be 97.50%.
Example 40
In an autoclave, 100.0g of geranylacetone, 5.0g of catalyst 3.0% Pd-7.0% Bi/BaCeO were added 3 L10 (catalyst mass concentration 5.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. After 3.5 hours of reaction, pressure is released, the reaction liquid is pressed out and filtered out of the catalyst, the reaction liquid is detected by gas chromatography, the geranyl acetone conversion rate is 99.52%, and the selectivity of dehydronerolidol is 98.37%.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 110.69g of a crude dehydronerolidol product was obtained, and the yield was calculated to be 97.61%.
Example 41
Into an autoclave, 100.0g of 6-methyl-5-octen-2-one, 5.0g of catalyst 5.0% Pd-7.0% Bi/BaCeO were added 3 L10 (catalyst mass concentration 5.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 3.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-octene-2-ketone is 99.72 percent, and the selectivity of dehydroethyl linalool is 98.58 percent.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 116.48g of crude dehydroethyl linalool was obtained, and the yield was 98.24%.
Example 42
In an autoclave, 100.0g of 6-methyl-5-octen-2-one, 1.0g of catalyst 5.0% Pd-7.0% Bi/BaCeO were added 3 L10 (catalyst mass concentration 1.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. After the reaction is carried out for 5.0 hours, the pressure is relieved, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-octene-2-ketone is 89.49%, and the selectivity of dehydroethyl linalool is 97.61%.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 103.43g of crude dehydroethyl linalool was obtained, and the yield was 87.23%.
Example 43
Into an autoclave, 100.0g of 6-methyl-5-hepten-2-one (content 98.5%) was added, 5.0g of catalyst 5.0% Pd-7.0% Bi/BaCeO 3 L10 (catalyst mass concentration 5.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting temperature to 60deg.C, reacting at constant temperature, maintaining acetylene pressure at 0.2 0MPa. The reaction is carried out for 5.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-hepten-2-one is 98.69%, the selectivity of dehydrolinalool is 97.74%, and the gas phase diagram of the reaction liquid is shown in figure 2.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials and raw materials were recovered to obtain 125.07g of crude dehydrolinalool, and the yield was calculated to be 96.37%.
Example 44
In an autoclave, 50.0g of formaldehyde, 5.0g of catalyst 5.0% Pd-7.0% Bi/BaCeO were added 3 L10 (catalyst mass concentration 5.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 30 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 4.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the formaldehyde conversion rate is 99.67%, and the propargyl alcohol selectivity is 98.38%.
The reaction mixture was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to give 91.41g of a crude propargyl alcohol product, and the yield was calculated to be 97.92%.
Example 45
100.0g of tetrahydrogeranylacetone, 10.0g of catalyst 7.0% Bi-9.0% Ce/BaCeO were added in an autoclave 3 L10 (catalyst mass concentration 10.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 40 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. After the reaction is carried out for 6.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of the tetrahydrogeranylacetone is 90.71 percent, and the selectivity of the tetrahydrodehydronerolidol is 89.64 percent.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 91.74g of a crude tetrahydrodehydronerolidol product was obtained, and the yield was 81.10%.
Example 46
In an autoclave, 100.0g of plant ketone, 10.0g of catalyst 7.0% Bi-9.0% Co/BaCeO were added 3 -L10 (the mass concentration of the catalyst is 10.0%), 100.0g of ethanol is replaced by nitrogen for 3 times, acetylene is introduced for 3 times, stirring is started, the temperature is set to 60 ℃, the constant temperature reaction is carried out, and the acetylene pressure is kept at 0.20MPa. After the reaction is carried out for 6.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the plant ketone conversion rate is 91.52 percent, and the selectivity of dehydroisophytol is 85.23 percent.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain crude dehydroisophytol 85.20, calculated as 77.67%.
Example 47
Into an autoclave, 100.0g of 6-methyl-5-octen-2-one, 10.0g of catalyst 5.0% Pd/BaCeO were added 3 L10 (catalyst mass concentration 10.0%), 100.0g ethanol, 3 times with nitrogen, 3 times with acetylene, stirring, setting the temperature to 60 ℃, reacting at constant temperature, and maintaining the acetylene pressure at 0.20MPa. The reaction is carried out for 6.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-octene-2-ketone is 89.82%, and the selectivity of dehydroethyl linalool is 86.29%.
The reaction solution was distilled under reduced pressure, and the solvent and unreacted raw materials were recovered to obtain 91.67g of crude dehydroethyl linalool, and the yield was 77.31%.
Comparative example 1
Into an autoclave, 100.0g of 6-methyl-5-octen-2-one, 10.0g of catalyst 9.0% Bi/BaCeO were added 3 (the mass concentration of the catalyst is 10.0%), 100.0g of ethanol is replaced by nitrogen for 3 times, acetylene is introduced for 3 times, stirring is started, the temperature is set to 60 ℃, the constant temperature reaction is carried out, and the acetylene pressure is kept at 0.20MPa. The reaction is carried out for 6.0 hours, the pressure is released, the reaction liquid is pressed out, the catalyst is filtered out, the reaction liquid is detected by gas chromatography, the conversion rate of 6-methyl-5-octene-2-ketone is 80.26%, and the selectivity of dehydroethyl linalool is 62.34%.
The reaction solution was distilled under reduced pressure, the solvent and unreacted raw materials were recovered, 58.72g of a crude dehydroethyl linalool was obtained, and the yield was 49.52%.
See table 1 for the above examples and comparative examples data:
table 1:
example 48
The catalyst recovered in example 43 was directly subjected to the experiment for the application of the catalyst, and the reaction conditions and the operation were the same as in example 43.
The experimental results are shown in table 2.
Table 2:
sleeve for jacket Substrate(s) Conversion rate Selectivity of Crude product amount Yield rate
1 6-methyl-5-hepten-2-one 98.69％ 97.75％ 125.03g 96.35％
2 6-methyl-5-hepten-2-one 98.58％ 97.66％ 124.74g 96.12％
3 6-methyl-5-hepten-2-one 98.60％ 97.67％ 124.81g 96.18％
4 6-methyl-5-hepten-2-one 98.46％ 97.61％ 124.58g 96.0％
It should be noted that, although the technical solution of the present invention is described in specific examples, those skilled in the art can understand that the present invention should not be limited thereto.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described. The terminology used herein was chosen in order to best explain the principles of the embodiments, the practical application, or the technical improvements in the marketplace, or to enable others of ordinary skill in the art to understand the embodiments disclosed herein.

Claims (10)

1. A catalyst for preparing alkynol by reacting carbonyl-containing compound with terminal alkynyl-containing compound, characterized in that,
the catalyst comprises a modifier and a metal oxide system, wherein the metal oxide system is a carrier oxide doped with a first metal element,
wherein,,
the modifier comprises a nitrogen-containing heterocyclic compound,
The first metal element includes one or more of Pd, ru, pt, nb, bi, cu and Co,
and, the modifier is present in at least a portion of the surface region of the metal oxide system.
2. The catalyst of claim 1, wherein the carbonyl-containing compound has a formula represented by the following formula (I):
wherein R is 1 、R 2 Each occurrence of which is the same or different and is each independently hydrogen or a monovalent organic group, or R 1 And R is 2 May be linked to form a ring, provided that R 1 、R 2 Not both hydrogen.
3. The catalyst according to claim 1 or 2, wherein the terminal alkynyl-containing compound has the formula (II),
≡-R 3
(II)
wherein R is 3 Is hydrogen or a monovalent organic group.
4. A catalyst according to any one of claims 1 to 3, wherein the nitrogen-containing heterocyclic compound is selected from one or more of pyridines, imidazoles, pyrazoles, quinolines, oxazolines.
5. The catalyst according to any one of claims 1 to 4, wherein the content of the first metal element in the metal oxide system is 0.1 to 10 mass% based on the mass of the doped carrier oxide.
6. The catalyst according to any one of claims 1 to 5, wherein the molar ratio of the nitrogen-containing heterocyclic compound to the first metal element in the catalyst is 10 to 20:1.
7. The catalyst according to any one of claims 1 to 6, wherein the first metal element comprises two or more elements of Pd, ru, pt, nb, bi, cu and Co.
8. A process for the preparation of alkynols, said process comprising:
a step of reacting a carbonyl-containing compound with an alkynyl-containing compound in the presence of the catalyst according to any one of claims 1 to 7, the reaction being carried out with or without the use of a solvent.
9. The method of claim 8, wherein the temperature of the reaction is 70 ℃ or less and the time of the reaction is 6 hours or less.
10. The method according to claim 8 or 9, wherein the catalyst is a freshly prepared catalyst or a reused catalyst.
CN202310595396.8A 2023-05-23 2023-05-23 Catalyst and process for alkynylation Pending CN116651451A (en)

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